In 2000, Flair made her first appearances in professional wrestling at the age of 13, appearing with her father in World Championship Wrestling (WCW) as Ashley Flair during his feud with Vince Russo and her half-brother David. On the May 15 episode of Monday Nitro, Flair appeared in a vignette in which Russo, David and Daffney invaded the Flair family home until being confronted by Flair, her mother Beth, and her brother Reid. At The Great American Bash on June 11, Flair was at ringside for a retirement match between Ric and David. After Russo attempted to interfere in the match on David's behalf, she and her brother Reid attacked him and handcuffed him, enabling their father to go on to defeat David. On the following evening's episode of Monday Nitro, David and Russo faced Ric in a handicap match with the Flair family once again at ringside. Flair attempted to interfere on her father's behalf, but was restrained by R&B Security, Russo's henchmen, allowing David and Russo to defeat Ric and partially shave his head.

Flair was arrested on September 5, 2008 in Chapel Hill, North Carolina for assaulting a police officer after a fight involving Flair, her then-boyfriend, and her father. She pleaded guilty to a lesser charge and was sentenced to 45 days in jail, which was suspended to supervised probation and a $200 fine.

On May 17, 2012, she signed a developmental contract with WWE and trained under Lodi in North Carolina before joining NXT, the WWE developmental territory, in Tampa, Florida. Her trainers in NXT included Sara Del Rey. Fliehr adopted the ring name Charlotte and had her first televised singles match on the July 17, 2013 episode of NXT, where she defeated Bayley.

In late 2013, Charlotte formed a tag team with Bayley, and the two defeated Aksana and Alicia Fox on the September 4 episode of NXT. On the October 10 episode of NXT, Bayley accompanied Charlotte to a match against Santana Garrett, which she won, but during the match The BFFs—Beautiful, Fierce Females (Sasha Banks and Summer Rae) came to the ring and attempted to convince Bayley to join them, much to Charlotte's annoyance. On the November 13 episode of NXT, Charlotte attacked Bayley and joined the BFFs, establishing herself as a villainess in the process.

On the July 13 episode of Raw, Stephanie McMahon called for a "revolution" in the Divas division, subsequently introducing the best Charlotte, Becky Lynch, and Sasha Banks as members of the main roster. Charlotte and Lynch allied with Paige, who was engaged in a feud with Team Bella (Alicia Fox and The Bella Twins), while Banks allied with Tamina and Naomi, starting a rivalry between the three teams. The trio of Charlotte, Lynch, and Paige was dubbed Team PCB after the first name initials of each Wrestler. On July 19 at Battleground, Charlotte defeated Banks and Brie Bella in a triple threat match in her WWE pay-per-view debut. The three teams would ultimately face off at SummerSlam in a three team elimination match, which Charlotte's team won after Lynch pinned Brie Bella. On the August 31 episode of Raw, Charlotte overcame fellow Team PCB members' records in the first ever Divas Beat the Clock challenge, and was named the new number one contender to Nikki Bella's Divas Championship. Her title match against Nikki Bella, initially advertised for Night of Champions, took place on the September 14 episode of Raw, so Charlotte could stop Bella from surpassing AJ Lee's record and becoming the longest-reigning Divas Champion. Charlotte won the match by disqualification after she pinned Brie due to the twins switching places, causing Nikki to retain her title. On September 20 at Night of Champions, Charlotte defeated Nikki in a rematch to win the Divas Championship for the first time. During Charlotte's celebration the following night on Raw, Paige cut a worked shoot promo and turned on her Charlotte and Lynch, berating them and the Divas division. Throughout October, Paige appeared to have reconciled with Lynch and Charlotte. Paige cemented her departure from the team by attacking both Charlotte and Lynch the night after Charlotte successfully retained her championship against Nikki at Hell in a Cell. Charlotte successfully defended her title against Paige on three different occasions—at Survivor Series on November 22, in a rematch the following night on Raw and at TLC: Tables, Ladders & Chairs on December 13.

She married Riki Johnson in May 2010 and they divorced in 2011. In Second Nature, a joint biography of her and her father released in late 2017, she revealed that she left Johnson after having been the victim of multiple domestic assaults. In 2013, Flair was married a second time to Thomas Latimer, better known by his ring name Bram. Their divorce was finalized on October 29, 2015 in the state of Florida.

Charlotte Flair's first reign was when the championship was called the WWE Women's Championship. As a result of the 2016 brand extension draft, which happened during her first reign, the title became exclusive to Raw. It was renamed to Raw Women's Championship during her second reign after SmackDown created the SmackDown Women's Championship.

Flair ranked 29th out of 50 in the 2017 Sports Illustrated. fittest woman athletes of the year.