A primetime British television programme will also present a fresh timeline of events surrounding the disappearance of the British girl from her family's holiday apartment, just a few days before her fourth birthday.
It will include a new 25-minute reconstruction as well as live interviews with Gerry and Kate McCann, who launched a global media campaign to find their daughter and still hold out hope she is alive.
Portuguese authorities closed their investigation in 2008, but London's Metropolitan Police spent two years reviewing the evidence and opened their own probe in July this year.
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Last week, the British force said analysis of mobile phone data from thousands of people who were in the south coast resort of Praia da Luz when Madeleine disappeared could provide a new lead.
The detectives have interviewed 442 people over the last couple of years and have identified 41 potential suspects -- 15 of them British nationals -- although no arrests have been made.
In the BBC's "Crimewatch" programme on Monday night, e-fits of men seen in and around Praia da Luz at the time will be published in a bid to identify them and eliminate innocent sightings.
"Primarily what we sought to do from the beginning is try and draw everything back to zero," said Detective Chief Inspector Andy Redwood, who is leading the probe, in a clip from the programme released to the media.
"Try and take everything back to the beginning and re-analyse and reassess everything, accepting nothing."
He said detectives were focused on the time between 8:30 pm on May 3, 2007, when Kate and Gerry McCann left the apartment to dine at a nearby tapas restaurant with friends, to when Kate McCann found Madeleine was missing at 10:00pm.
"Our work to date has significantly changed the timeline and the accepted version of events that has been in the public domain to date," Redwood added.
The appeal will be shown in Germany and the Netherlands after Monday's broadcast in Britain.
Last week the McCanns said they were "greatly encouraged by new information coming to light" and said they hoped the appeal would take them closer to find Madeleine.
In another clip released from the forthcoming programme, the McCanns speak about how much they miss their daughter.
"When it's a special occasion, when you should be your happiest and Madeleine's not there, that's when it really hits home," said Gerry McCann.
"Obviously, Madeleine's birthday goes without saying."
Kate McCann added: "It's when you have big family occasions really. That's it, isn't it? 'Family occasion' and you haven't got your complete family."
