They say some residents have resorted to eating grass.
Medical charity group, Doctors Without Borders says 16 people have died there despite United Nations aid convoys reaching the town earlier this month.
World Food Programme spokeswoman, Bettina Luescher, said at the same briefing that it was extremely difficult to deliver aid in the country, adding there are 18 siege locations across Syria, including in areas controlled by the government, Islamic State militants and other insurgent groups.
Dozens of deaths from starvation have been reported by monitoring groups, local doctors, and aid agencies from Madaya, a town under siege where residents said they resorted to eating grass.
"The latest numbers are 18 besieged areas, more than 4.6 million people that have not... either that have been in besieged areas or in hard to reach areas. Those are the latest numbers that we have received from the people on the ground. Once again WFP is appealing that all the humanitarian actors, all the humanitarian organizations get access to those areas so we can deliver life saving aid and food, water, medicine and other things," Luescher said.
She added that delivering aid was difficult.
"That is a very hard thing to pull off. You need to have first of all a safe air space. Our planes cannot go and fly somewhere if the airspace is not safe. The second thing you would need for an air drop is you need to have a secured area on the ground, a wide area where people are being kept away so that air drops, for example the larger packages that one throws out of air planes, can land safely," she said.
Main Syrian opposition team arrives in Geneva
A delegation from Syria's main opposition group arrived in Geneva on Saturday to assess whether to join Damascus government officials in United Nations-brokered peace talks.
The 17-strong team included the head of the Saudi-backed Higher Negotiation Committee (HNC), which includes political and militant opponents of Syrian President Bashar al-Assad in the country's five-year-old civil war, an opposition spokesperson said.
The HNC has said it wants to discuss humanitarian issues including a stop to Russian and Syrian government bombing before engaging in the peace talks that started on Friday in Geneva.
Russian air strikes on Syria have killed nearly 1,400 civilians since Moscow started its aerial campaign nearly four months ago, the Syrian Observatory for Human Rights, a monitoring group, said on Saturday.
"We are going to Geneva to put to the test the seriousness of the international community in its promises to the Syrian people and to also test the seriousness of the regime in implementing its humanitarian obligations," Riyad Naasan Agha said.
"We want to show the world our seriousness in moving towards negotiations to find a political solution," he told Reuters.
French Foreign Minister Laurent Fabius said on Saturday the Geneva talks must ensure human rights are upheld as participants work towards a political transition in Syria.
"Humanitarian law must be respected and the objective of a political transition actively pursued to enable the talks to succeed," Fabius said in a statement sent to Reuters.
Russian Deputy Foreign Minister Gennady Gatilov was quoted by Russian Interfax news agency as saying that no direct talks were expected in Geneva, only proxy talks.
Gatilov, whose country has also objected to the opposition's composition saying it included groups that it deemed as terrorist, said there were no preconditions for the Syrian talks and that Moscow welcomed the decision by Syrian opposition coordinator, Riad Hijab, to take part in talks in Geneva.
UN sets out aims
The United Nations earlier said the aim would be six months of talks, first seeking a ceasefire, later working toward a political settlement to a war that has killed more than 250,000 people, driven more than 10 million from their homes and drawn in global powers
German Foreign Minister Frank-Walter Steinmeier told the German newspaper Welt am Sonntag: "Only at the negotiating table will it become clear if both sides are prepared to make painful compromises so that the killing stops and Syrians have a chance of a better future in their own country."
The HNC's demands include allowing aid convoys into rebel-held besieged areas where tens of thousands are living in dire conditions, Agha said.
The medical charity Medecins Sans Frontieres (MSF) said on Saturday that 16 people had starved to death in the government-besieged town of Madaya since aid convoys arrived this month and accused the authorities of blocking medical shipments.
“It is totally unacceptable that people continue to die from starvation, and that critical medical cases remain in the town when they should have been evacuated weeks ago,” said Brice de le Vingne, MSF’s director of operations in a statement.
Agha said the opposition delegation, including HNC head Hijab and chief negotiator Asaad al-Zoubi, would not call for a complete cessation of hostilities but would demand an end to "the indiscriminate shelling of markets, hospitals and schools by the regime and its Russian backers".
Russia and Syria deny targeting civilians, saying they take great care to avoid bombing residential areas.
Separately, the heavy Russian bombing campaign continued unabated in northern Syria on Saturday with the Syrian Observatory for Human Rights saying the areas hit included rebel-held villages and towns in the Aleppo countryside near the border with Turkey.
Air strikes and shelling
Russian air strikes were also reported by the group in Hama province and in the eastern province of Deir al Zor where scores of people were killed in the aerial attacks on Islamic State- controlled towns in the territory that also borders Iraq, according to residents.
At least 40 people, including women and children, were injured when the army shelled a camp where over 3,000 displaced people had taken shelter, according to a rebel spokesperson from the First Coastal Division brigade who spoke from the area along the Turkish border in northwestern Latakia.
Heavy clashes also continued in the Latakia countryside where the Syrian army backed by intensive Russian carpet bombing in the rugged mountainous area allowed the government to regain most of the countryside close to the coastal heartland of Assad's Alawite sect.
In separate comments before heading to Geneva, Zoubi said they would not engage in any negotiations before goodwill measures were taken. These had to include a halt to bombing of civilian areas.
"Without concrete steps, Geneva would be futile" he told Reuters.
He said US Secretary of State John Kerry gave assurances by phone to the HNC's leadership, saying Washington supported a U.N.-backed political transition period without Assad, a bone of contention among warring parties.
The HNC has also been under pressure from mainstream armed groups represented within it not to give in to Western pressure, with some rebel groups already threatening to pull out of the body.
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