Peake and US colleague Tim Kopra switched their spacesuits on to battery power at 7:48 am (1248 GMT), marking the official start of the floating debut for Peake, who is also the first British astronaut to fly to the orbiting International Space Station.
In a blog post on Thursday, Peake said he felt "exhilarated" but had "no time to dwell on these emotions."
The 43-year-old Peake's job is to haul a bulky component called a sequential shunt unit, contained in a white bag as big as a suitcase.
Kopra, 52, making his third career spacewalk, will carry the tools needed to remove the old unit and replace it with the new one.
The work must be precisely timed to coincide with a nighttime pass of the space station to avoid any sparks from electrical current that might remain in the solar-powered equipment.
The ISS circles the Earth every 90 minutes, and spends 31 of those minutes in the dark.
Afterward, they will route some cable and install a vent in a cramped space that spacewalk officer Paul Dum described this week as a "challenging work site."
Writing on his blog, Peake said he had done months of training while on Earth for the mission, including virtual reality sessions to train "for the worst-case scenario of becoming detached from the space station."
Each step of the six-and-a-half hour spacewalk has been "meticulously planned," he added.
"But I guess nothing can prepare for the feeling of being outside of a spacecraft in the vacuum of space.
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