In addition to material from Morissette's first two U.S. albums, MTV Unplugged featured performances of "No Pressure over Cappuccino" and "Princes Familiar", two previously unreleased songs from her tours, and "These R the Thoughts", a previously released b-side. Morissette has stated that "Princes Familiar" in particular is one of her favorite and most vocally challenging songs. She performed it on her 2005 Diamond Wink Tour, where she dedicated it to "all of the dads in the audience." The ballad "No Pressure over Cappuccino", one of the first songs she wrote following the release of Jagged Little Pill, is presumably about the singer's twin brother, Wade.
Featuring cleaner vocals, slower arrangements and a few drastic reinventions (particularly in the case of "You Oughta Know"), MTV Unplugged foreshadowed much of Morissette's later, softer work, particularly 2005's Jagged Little Pill Acoustic and the accompanying Diamond Wink Tour.
MTV Unplugged is Alanis's best-selling album in Brazil.