I believe Darlene actually sang lead on He's a Rebel but never performed live with the Crystals
From Wikipedia:
The "Replacement" Crystals
Soon after "He Hit Me" flopped, Phil Spector began recording singer Darlene Love and her backing group The Blossoms under the name "The Crystals". Legend has it that the real Crystals were not able to travel from New York to Los Angeles fast enough to suit the LA-based Spector, who wanted to quickly record and release "He's a Rebel" (written by Gene Pitney) before anyone else had a chance to cover it and have a hit with it. A version recorded by Vikki Carr was about to be released, for example. The Crystals were unavailable, but Love and the Blossoms were also based in LA, so Spector recorded them and put the record out under The Crystals' banner.
"He's A Rebel" is perhaps the Crystals' most well-remembered and beloved song, and one of the most enduring of the girl group genre. It was also their only US #1 hit. The follow-up Crystals single, "He's Sure the Boy I Love", in actuality also featured Love and The Blossoms. It reached a very respectable #11 on the Billboard chart, and features a classic spoken intro by Darlene Love.