The deal runs from 2012 to 2015. ITV, for an outlay believed to be close to £160m, will show 18 games per season, plus the Uefa Super Cup, in which the Champions League winners take on the Europa Cup winners.
According to an ITV spokesman, the switch back to Tuesday was made with a view to having more consistent scheduling, given that most international football games are held on Tuesday nights.
ITV has also secured enhanced new media rights, giving it the ability to sell advertising against online and mobile Champions League content.
It will be able to broadcast matches on demand and show clips of all matches on mobile and video-on-demand.
According to ITV, audiences for this year's knockout phase of the tournament have averaged 6.3 million viewers so far.
Sky Sports will show 129 live Champions League matches each year, plus the Uefa Super Cup.
It will have exclusive live rights to all Wednesday night games and all Tuesday night games, barring ITV's pick.
In addition to live rights and highlights, Sky Sports has also been awarded cross-platform rights for use on mobile and broadband.
Matches will be offered live on PC or laptop through Sky Player at www.skysports.com and on mobile devices through Sky Mobile TV.
In February EU advocate general Juliane Kokott said blocking foreign satellite feeds breached EU laws and Sky and ESPN cannot prevent customers watching Premiership football from foreign satellite feeds.
The European Court of Justice (ECJ) will make a ruling on the matter later this year.
The deal with Uefa comes ahead of Sky's latest quarterly results tomorrow. Analysts expect the company to have picked up around 40,000 new subscribers with the help of its HD offering.