In the three-season deal, ITV has secured exclusive rights to 16 first-choice Champions League games on Tuesdays, along with a highlights package.
The broadcaster will air live coverage of the Champions League final and the UEFA Super Cup at the same time as Sky. It will also stream coverage on mobiles and on ITV.com.
Sky Sports will be able to show 129 live Champions League matches each season, including all Wednesday games and Tuesday matches, apart from ITV's first pick.
The new deal will enable Sky to broadcast up to 15 live matches each week, including the qualifying rounds before the group stage begins. In addition to live rights and highlights, Sky will also offer online and mobile coverage via Sky Player and Sky Mobile TV.
Barney Francis, managing director of Sky Sports, said that the satellite broadcaster offers the "most comprehensive coverage" of the Champions League.
"We introduced the exceptional quality of HD, then increased the number of live matches and have now pioneered 3D broadcasts," said Francis.
"The UEFA Champions League goes from strength to strength and we look forward to extending our relationship with UEFA."
Guy-Laurent Epstein, marketing director of UEFA Events, said: "The renewal with ITV and Sky Sports will deliver extensive coverage of the UEFA Champions League across all broadcast platforms guaranteeing that it is widely accessible to all football fans throughout the United Kingdom. UEFA is delighted to maintain and further extend its current successful relationship with ITV and Sky Sports until 2015."
ITV controller of sport Niall Sloane added: "The UEFA Champions League continues to set the benchmark for sports competitions across the world and has been a hugely successful part of the ITV1 schedule over many years.
"We're delighted to be extending this long relationship and to have agreed a new deal in which ITV1 will continue to broadcast the competition free-to-air, and ITV will also have increased opportunities to bring the Champions League to viewers across our online and on-demand platforms."
Sky yesterday announced that ESPN's 3D coverage of the 2011 FA Cup Final will air on the Sky 3D channel next month.
Former Manchester United defender Gary Neville will join Sky Sports next season as a replacement for Andy Gray, who was sacked by the broadcaster in January after a sexism storm.