Wolfe grew up in Oberlin, Louisiana and spent part of her childhood in Los Angeles. She moved from Oberlin to Austin Texas in 1996 with her two daughters. After being homeless and working construction, she met her original trainer 'Pops' Billingsley. She fought her amateur fights under Billingsley's tutelage and started fighting as a professional for RPM Promotions. Wolfe has mentored many children through her gyms, now lives in Austin and is a business-owner.

Ann had a record of 3-1 as an amateur boxer and fought at the 1998 U.S. National Championships. She won a decision over Tami Hendrickson of Seattle in the quarter-final by 50-39, then went on to stop Shanie Keelean of Chicago within 46 seconds of the first round. In the semifinal Wolfe lost to La'Kiea Coffen by a disqualification at 1:23 of the third round.

On May 8, 2004, she emulated Henry Armstrong's record of three world titles at the same time in different weight classes, by gaining the IBA world Light Heavyweight championship, knocking undefeated champion and former NCAA basketball star Vonda Ward at one minute and eight seconds of Round One. Ward had a neck concussion because she hit the canvas with her neck when she fell. Ward was taken to the hospital in serious condition due to damage to her neck and head, but she recuperated. This bout was nationally televised from Biloxi, Mississippi and television commentators called it "the best knockout punch ... in a women boxing match".

On August 20, 2005, she fought and defeated Valerie Mahfood for the second time, by a ten round decision.

Wolfe last fought in 2006, knocking out Cassandra Giger and decisioning Lisa Ested. Since then, she has indicated that she is finished with her own boxing, preferring to work as a trainer.