The six-year contract, which does not include naming rights for the home of English football, begins with immediate effect.
Last year it was reported the Football Association, who own the stadium, were contemplating selling naming rights to the ground similar to Arsenal's association with Emirates and Manchester City's deal with Etihad.
But in a statement, the game's governing body in England stressed the iconic name of the world-renowned stadium would remain.
The deal will see EE provide enhanced 4G coverage, super-fast wi-fi and mobile payment solutions for fans attending the venue which is used for a number of sports and concerts.
Wembley chairman Melvin Benn said: "Wembley Stadium marked its 90th
anniversary in 2013 and this partnership shows that we're looking to the future.
"We are ensuring we fulfil our ambition to offer inspiring memories, whilst
bringing innovation to the stadium at a much faster rate and providing services
that are at the forefront of consumer engagement and technology.
"As stadia around the world become increasingly more technologically advanced, EE is the perfect partner to assist us in fulfilling that goal, giving event owners and their fans the best possible and unforgettable shared experiences."
EE chief executive Olaf Swantee said: "We are extremely proud to announce our partnership with Wembley Stadium. We are always looking for new ways to enhance digital lives across the UK and this ground-breaking deal allows us to extend the same vision and passion to the country's national stadium.
"Over the coming months, we will announce an exciting programme of upgrades and innovations to the existing infrastructure at Wembley that will ensure the stadium offers visitors a world class spectator experience for many years to come."