The collection includes audiobooks, exclusive podcasts and music videos related to this year's fund-raising campaign.
Also available is this year's charity single, a cover of classic Run DMC/Aerosmith track 'Walk This Way' by the Sugababes and Girls Aloud.
The official video sees both bands paying homage to the classic Run DMC and Aerosmith video before they battle each other on the catwalk with the help of some of the UK's hottest comedy talent.
Further exclusive material will be made available through the iTunes Store from the Red Nose Day festivities as Comic Relief releases comedy footage, plus "something very special from Peter Kay".
Additional Red Nose Day content includes podcasts from Chris Moyles, Chris Evans and the Sugababes v Girls Aloud podcast special. Apple has also put together a collection consisting of all previously released Comic Relief charity releases dating back to 1995.
Net profits from this year's official singles and videos will go to Comic Relief.