She has won three Olympic gold medals with Team USA and was inducted into the NYC Basketball Hall of Fame at the head of the Class of 2024 - the first female to head a class at any major basketball hall of fame and the first active player ever inducted.

[6] She participated in the 2006 WBCA High School All-America Game, where she scored fifteen points and had twelve rebounds.

[8] During high school, Charles also played on the AAU club basketball team the New York Gazelles.

On March 1, 2010, during a game against Notre Dame, Charles broke two UConn records on the same night.

Additionally, Charles started the night in third place in career scoring, behind Kerry Bascom and Nykesha Sales.

In 2010, she spent six hours a week as an intern at Bergin Correctional Institution, helping prisoners adjust back to life in society.

The coach did put her back in the game in the fourth quarter, and she earned an assist on a pass to Jessica Moore, leading to the triple double.

She led the league in the number of double-doubles recorded, and set the mark for the fastest player in WNBA history to reach 900, 1,000 and 1,100 rebounds.

In 2016, Charles had the best season of her career, averaging a career-high 21.5 points per game while shooting 43.9% from the field and 81.2% from the free-throw line.

With the WNBA's new playoff format in effect, the Liberty were the number 3 seed in the league with a bye to the second round with one elimination game to play where they were defeated by the Phoenix Mercury.

[21] The Liberty would once again finish with number 3 seed in the league, receiving a bye to the second round elimination game.

[25] Charles was medically excused for the shortened 2020 season on July 17, 2020, due to her condition with extrinsic asthma, which impacts her immune system and put her at risk in the coronavirus pandemic.

[26] Since 2013, Charles has donated her full WNBA salary to the charity she started, Hopey's Heart Foundation.

In 2020, Charles announced she would direct that year's salary to support the Black Lives Matter movement.

On June 25, 2022, Charles and the Mercury agreed to a buyout from her contract - officially ending her time in Phoenix.

Charles helped set the tone in the opening game against Paraguay, recording a double-double with 20 points and 10 rebounds.

[36][37] Charles was named a member of the team representing the US at the 2009 World University Games held in Belgrade, Serbia.

[38] On October 5, 2009, Charles was selected to be one of the USA National Team members to travel to the 2009 Ekaterinburg International Invitational.

[40] Charles was named the USA Basketball 2009 Female Athlete Of The Year, for her contributions to the Gold Medal earned at the 2009 USA Women's World University Games, the Gold Medal earned at the 2009 Ekaterinburg International Invitational, and the undefeated collegiate season leading to a National Championship.

[43] Charles was selected to be a member of the National team representing the US at the World Championships held in September and October 2010.

Several players shared scoring honors, with Swin Cash, Angel McCoughtry, Maya Moore, Diana Taurasi, Lindsay Whalen, and Sylvia Fowles all ending as high scorer in the first few games.

The USA team had only a five-point lead at halftime, which was cut to three points, but the Czechs never got closer.

Charles played for Team USA during the 2016 Summer Olympics, helping them win their sixth gold medal as they defeated Spain 101–72.