At 01:00 GMT (07:00 local time), the Soyuz launcher was rolled out on its flat-bed transporter for the 2km train journey to the pad.
The train took almost two hours to reach the pad, known as Site No 1.
Mr Peake will be accompanied by American Tim Kopra and Russian Yuri Malenchenko on Tuesday’s flight to the International Space Station (ISS).
It should take the astronauts about six hours to reach the orbiting outpost, where they will dock and join the crew of three already stationed there.
Astronauts’ relatives, members of the back-up crew, space agency officials and journalists were among the visitors gathered to see the rocket rolled out of its hangar and lifted to the vertical position at the launch site where Yuri Gagarin became the first human to blast into space in 1961.
Among them were Tim Peake’s parents, Angela and Nigel.
Angela Peake told BBC News it was “fantastic” to be at Baikonur for her son’s launch, adding she was immensely proud of him.
Nigel Peake said: “[Tim] is raring to go now. He’s trained, he’s ready, he’s happy. They’re all together and just waiting for the big lift-off.”
He added he was “a bit over-awed” at the “scale of the operation”.
German-born Alexander Gerst, who was one of the other five European Space Agency (Esa) astronauts selected along with Mr Peake in 2009, told me: “I met Tim yesterday, he’s in very good spirits, and he’s looking forward to it.”
Mr Gerst, who flew to the ISS in 2014, added: “It’s going to be an amazing ride for him – I’m jealous! He really deserves his flight, but I told him: ‘If you have another seat up there in the spaceship I’ll come with you.”
It was a bitterly cold morning here at Baikonur Cosmodrome, as a diesel locomotive was backed up to the door of the giant hangar-like facility known as Building 112, in readiness to haul the rocket along a railway track to its destination.
As the shutters lifted in the darkness, revealing the building’s illuminated interior, there was excitement as the crowd glimpsed the red nozzles and polished metal of the Soyuz rocket’s “business end”. The locomotive sounded its whistle and sped past us, with the launcher and its transporter in tow.
We then decamped to a railway crossing, trudging across the hard-frozen ground to watch the last leg of this carefully choreographed performance as the launcher advanced down the final stretch of track to the launch site known informally as Gagarin’s Start.
Once it arrived, the rocket was to be raised up and encased within the arms of its service structure.