The Belgian, who competed for Marussia Virgin during the 2011 campaign, will join Dragon Racing for the all-electric single-seater series, which kicks of in Beijing in September.
29-year-old D'Ambrosio joins sometime IndyCar and WEC ace Mike Conway at the American squad; Sebastien Bourdais and Oriol Servia are also on the team's roster, though it is not yet clear whether this will involve them contesting any races.
“It is with great excitement that I will be at the wheel of the Dragon Racing entry in this historic first season of the FIA Formula E Championship,” said D'Ambrosio.
“I have watched the Dragon Racing organisation closely over the last few months and feel that together we can achieve great results during this first season.”
Team boss Jay Penske was also pleased to have firmed up the deal.
"After watching Jerome’s performances in F1, as well as the most recent Formula E test, I feel that the combination of Jerome and our other drivers should prove to be a formidable force.”
D'Ambrosio is the 10th driver with F1 experience to commit to the series. Just three seats on the grid are yet to be filled, with the championship set to kick off on September 13.