All Tuesday night matches - other than the two scheduled on ITV - will also be exclusively live on Sky.
Under the three-year deal, Sky will show 14 matches exclusively live from each week of the Group Stage with viewers able to pick their live game - or switch between games - by using Sky digital's interactive service.
On Wednesday evenings each of the eight UEFA Champions League matches will be exclusively live on Sky via an interactive menu.
On Tuesday evenings there will be six exclusively live Champions League matches on Sky's interactive service, with two shown live on ITV.
Sky will continue to have exclusive live coverage of all Wednesday night games up to and including the Semi-Finals. The Final will be live on both Sky and ITV.
Commenting on the new deal, Vic Wakeling, Managing Director of Sky Sports, said: "The Champions League has broadened the horizons of football fans - far beyond the game's traditional and local base - and this is a dream offering, made possible only by the unique interactive capacity of Sky digital.
"Every single game played in the competition will now be seen live in the UK and, as fans ourselves, we are excited at the prospect of being involved in this new era of Champions League coverage."
Sky digital viewers will simply push the red button on their digital remote to see a list of live matches on offer. They can press 'select' to see a match full-screen then 'backup' to return to the menu and choose another live match.
