The French team has built its squad around the pair while also putting "a strong emphasis on youth" with Canadian David Veilleux and Frenchmen Kevin Reza and Jerome Cousin all making their debut.
"They have all reached maturity having made regular progression within the team," said directeur sportif Sebastien Joly. "We're keen to help them continue to progress by testing them with a three-week stage race of this calibre. Besides, they're not exactly novices – each one of them has already taken part in big races."
Team Europcar, UCI Professional Continental, received one of three wildcards for the Tour de France, along with Cofidis and Sojasun.
Voeckler, 2012's mountains classification winner, will be given free reign while Rolland the team's general classification leader took out the Alpe d'Huez stage in 2011 before winning the young rider classification. Last year Rolland finished eighth overall and this year he is targeting a top-five performance. He was cleared to return to racing last week after he had been requested to hand back his licence for eight days after he recorded abnormally low levels of cortisol in a test carried out in conjunction with the MPCC (Movement for Credible Cycling) on the final weekend of the Critérium du Dauphiné.
Thirty-four year-old Voeckler this month won the sixth stage to Grenoble at the Critérium du Dauphiné and more recently won the Route du Sud.
Shepherding Voeckler and Rolland will be new Japanese national champion Yukiya Arashiro, Italy's Davide Malacarne and Frenchmen Cyril Gautier and Yohann Gene.
The full Europcar team for the Tour de France: Pierre Rolland, Thomas Voeckler, David Veilleux, Kevin Reza, Jerome Cousin, Yukiya Arashiro, Davide Malacarne, Cyril Gautier and Yohann Gene.