The first of its new Celestia trains will enter service in 2031, becoming the first double-deckers to operate in the UK and via the Channel Tunnel.
The 200-metre-long trains will be able to operate across all five countries served by Eurostar, and also to its planned new destinations Geneva and Frankfurt.
Alstom will build the new Celestia trainsets, named by members of the Eurostar team, which will increase seat capacity per train by 20% to 540, subject to final design specifications.
It means when services are running in a 400-metre formation, as they do via the Channel Tunnel today, services will feature more than 1,000 seats.
The first new trains are due to join the Eurostar fleet in January 2031, with an initial six entering commercial service in May the same year.
The new trains will operate alongside Eurostar's current fleet of 17 E320 trains, and upon delivery of the full order, will expand Eurostar's fleet to 67.
Eurostar plans to maintain the fleet at its Temple Mills depot in London, in which it will invest £80 million to accommodate the new trains, creating around 350 new skilled jobs.
It claims the Celestia trains will be the most sustainable it has ever operated featuring 97% recyclable components, with 25% made from recycled materials, while delivering energy savings of 20-50% compared with the current fleet.
“Placing this milestone order marks the concrete realisation of Eurostar’s ambitious growth strategy - to reach 30 million passengers by investing in a brand-new fleet," said Eurostar chief executive Gwendoline Cazenave. "We’re particularly proud to bring double-decker trains to the UK for the very first time.
"This is a golden age for international sustainable travel – and Eurostar is leading the race."