The publisher will distribute digital editions of its 80 top graphic novels through the platform.
This follows the November launch of publications through Barnes and Noble's Nook Tablet device, which Marvel had previously said was only a temporary exclusive arrangement.
"Marvel is taking the world of comics by storm and releasing a massive selection of our best and brightest graphic novels on the iBookstore," said Peter Phillips, senior vice president and general manager of Marvel Digital Media Group.
"For the first time ever, fans will be able to easily find and enjoy all of their favourite heroes including The Avengers, Spider-Man and the X-Men on iPad, iPhone, and iPod touch - one of the best digital platforms for reading comics and graphic novels."
The list of titles includes tie-ins such as Stephen King's Dark Tower and Castle: Richard Castle's Deadly Storm, classic tales such as the Infinity Gauntlet and Secret War and more recent major events including Secret Invasion and Siege.
Marvel is due to finish rolling out its digital and print same-day releases by the end of March.