But the ongoing fighting has cast a fresh shadow on the negotiations as dozens were killed in multiple bomb attacks in the Syrian capital, Damascus, claimed by IS militants.
Opposition representatives warn they may walk away from the discussions unless humanitarian conditions improve, while the Syrian government delegation says the blasts in Damascus merely confirm a link between the opposition and terrorism.
United Nations-sponsored talks to end the violence in Syria commenced with a shaky start in Geneva after a triple bomb attack in the Syrian capital, Damascus.
The deadly attack, claimed by the self-proclaimed Islamic State, occurred at a revered Shi'ite shrine.
It happened as government and opposition delegations convened in Geneva in a bid to start peace talks - the first in two years.
The UN's special envoy to Syria, Staffan de Mistura, met a Syrian opposition group, the so-called Higher Negotiation Committee (HNC), for the first time, calling it a useful meeting.
"They've been exchanging with me some of their own ideas and how they can be part of this exercise. And I am optimistic and determined because this is a historic occasion not to be missed."
Salim al-Muslat is the spokesman for the Saudi-backed HNC.
He says the group is seeking a solution for all Syrians and is demanding action on humanitarian issues.
"It's important for us to see that food goes to our children who are starved to death. To see Syrian families, Syrian women are safe sitting in their homes, in their houses, away from the strikes of the Russians. It is important for us that those women in the jails of (Syrian President Bashar al-) Assad are released."
The 17-strong HNC delegation wants a halt to attacks on civilian areas, the release of detainees and a lifting of blockades.
HNC delegate Bassma Kodmani has repeated the group's intention to attend the talks.
"We want to stress that we only came to Geneva after we had received assurances and a commitment, we have written commitments and we have a very precise commitment on the fact that there would be serious progress on the humanitarian issues. That is what allows this group to be here, not yet for negotiations, but certainly to set the ground for negotiations."
The head of the Syrian government delegation, Bashar Jaafari, says the opposition is not serious about the peace process and is trying to derail the talks with preconditions.
Mr Jaafari says the government is considering moves such as the creation of humanitarian corridors, ceasefires and prisoner releases.
However he suggested they might come about as a result of the discussions, not before them.
Mr Jaafari has also condemned the bombing at a shrine in Damascus saying the blasts confirm the link between the opposition and terrorists.
Asked if the Syrian government delegation would hold talks with the Islamist group Jaish al-Islam, Mr Jaafari said the delegation would not communicate with what he called "terrorists".
"We are not holding talks with individuals. We are not holding talks with terrorists. This is exactly why the special envoy insisted on having indirect talks. This is precisely why we don't know yet the names and the compositions of other side's delegation. We don't deal with terrorists."
Meanwhile, United States Secretary of State John Kerry has appealed to both sides to continue negotiations in Geneva.
He has also called for immediate steps by all the parties to get food aid and other humanitarian assistance to Syrians.
"Let me be clear. The Syrian regime has a fundamental responsibility. All the parties to the conflict have a duty to facilitate humanitarian access to populations in desperate need. The world needs to push in one direction toward stopping the oppression and suffering of the Syrian people and ending - not prolonging - this war."
The United Nations is aiming for six months of negotiations, first seeking a ceasefire, later working toward a political settlement to the civil war.
The conflict has killed over 250,000 people, driven more than 10 million others from their homes and drawn in global powers.
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