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.
Wolfe made her professional debut by beating Brenda Lee Bell by a four round decision. Her first and only career loss came four fights later, when she was knocked out in three rounds by veteran and future world champion Valerie Mahfood.
Wolfe beat Vienna Williams by a ten round decision to win her first world title, the IFBA Jr. Middleweight title. She beat Gina Nicholas by knockout in three to win the vacant WIBA Light Middleweight title. She then proceeded to beat Shirvelle Williams by knockout in one round on a non title bout.
Next was the vacant IFBA world Super Middleweight title, which she picked up by knocking out Marsha Valley in six rounds. She and Valley fought again, this time with the vacant WIBC's version of the title, and Wolfe won by knockout in round ten.
She avenged her defeat against Mahfood by taking the NABA World Super Middleweight Championship from her with a ten round decision.
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".
Wolfe retained her title in a rematch with Valley, by a sixth round knockout.
On July 19, 2005, Wolfe defeated Monica Nunez by a seventh round knockout in Lula, Mississippi.
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.
Wolfe has trained many amateur and professional boxers, including her oldest daughter Jennifer Fenn and light middleweight contender James Kirkland.
Wolfe was cast by Wonder Woman director Patty Jenkins in the supporting role of the Amazon warrior Artemis.