Aguilera is to team with Jennifer Hudson to honour the legacy of the late Donna Summer, while Dave Grohl and Taylor Hawkins of Foo Fighters are inducting Canadian band Rush.
Singer-songwriter Randy Newman is joining the Rock and Roll Hall of Fame as well this year and will be inducted by The Eagles singer Don Henley.
John Mayer and blues guitarist Gary Clark Jr are also performing a salute to blues musician Albert King.
Presenters for additional inductees Public Enemy, Heart, Quincy Jones and Lou Adler will be announced in the coming weeks.
Chuck D of Public Enemy recently hailed the rap group's induction into the Rock and Roll Hall of Fame as a victory for hip-hop.
"Us going in is a win for our peers like Kurtis Blow or KRS-One, Queen Latifah and [the already-inducted] Run DMC, the Beastie Boys, Grandmaster Flash & the Furious 5," Chuck D said.
"They're our peers, and I feel thankful we're joining that list, but also we look to shine the light on so many others and tell them that this is their induction, too."
The 2013 Rock and Roll Hall of Fame induction ceremony is held on April 18 at the Nokia Theatre L.A. LIVE in Los Angeles.
HBO will broadcast highlights on May 18.
Watch Donna Summer perform 'On the Radio' below: