The French manufacturer, an offshoot of the Citroen brand, was previously in partnership with the Techeetah team throughout the Gen2 era and won two drivers' and teams' champions apiece with the Chinese-owned squad.
But with significant uncertainty over the commitment of SECA, the Chinese media conglomerate in charge of Techeetah, DS has parted ways with the team and moves its attentions to the Dragon Penske squad - owned by Jay Penske, son of Team Penske and IndyCar CEO Roger.
Vergne continues his Stellantis ties to stay with DS, dovetailing that with a drive at Peugeot's World Endurance Championship Hypercar project, while 2021-22 title winner Vandoorne moves teams after three years with the departing Mercedes team.
DS director of performance Thomas Chevaucher, who also moves over from Techeetah, says that the marque is "eager" to begin a successful partnership with the team formerly known as Dragon.
"The start of a new association is always a big moment, and all of us at DS Performance are eager to begin this new adventure with Penske Autosport," said Chevaucher.
"We are starting this partnership in the best possible way by having two champions in the team!
"Thanks to Stoffel and Jean-Eric, we probably have one of the best line-ups and also the fastest pairing on the grid.
"With the powertrain and software expertise of DS Performance, we are now in an ideal position to continue our hunt for victories and titles."
Penske added: "We’re thrilled to partner with DS Automobiles, an iconic automotive brand who shares our ambitions in striving for excellence.
"This is a major milestone for our team, and something we have been looking forward to for years. Together we will push the technological boundaries in our hunt for performance and wins.
"With world champion driver Stoffel and two-time champion Jean-Eric, I am confident that we have one of the strongest line-ups on the grid!"
Dragon finished the previous season with just two points, courtesy of Sergio Sette Camara's heroics in London. An initial coup in signing Antonio Giovinazzi from Alfa Romeo's Formula 1 team was unable to bear fruit as the Italian failed to score.
Sette Camara has since departed the team for NIO 333, while Giovinazzi is a contender for a Haas F1 seat having maintained ties with Ferrari.
The Dragon Penske team has previously won two races in Formula E, with a win in both of the first two seasons thanks to Jerome D'Ambrosio - who has recently left his team principal role at Maserati.
Dragon placed second in the first ever teams' championship, but a steady slide means that it has finished 11th in each of the last three seasons.
Before joining Techeetah, DS also supplied powertrains to the Virgin - now Envision - team during the Gen1 era.