Charley joined Woburn Golf Club at the age of 11 and frequently represented the Woburn ladies teams, partnering fellow member, Lauren Taylor in the scratch league matches. Charley won the Woburn Ladies Club Championship in 2010 with a record score of 7 under on the Duke's and Duchess' courses.
Charley enjoyed a very successful career as an amateur. In 2010 Charley and Lauren partnered each other when they represented Europe in the Junior Solheim Cup, in which it was a unique achievement for a golf club to have two members playing together. In 2012 Charley represented England in the Home Internationals and was also a member of the victorious Great Britain & Ireland team in the Curtis Cup.
Having turned professional at the end of 2012, Charley had a fantastic first season, which included representing Europe as the youngest ever player in the Solheim Cup, defeating Paula Creamer by 5 & 4 in the singles which helped Europe to victory. The year culminated with her winning Rookie of the Year and also finishing 6th in the LET Order of Merit.
In March 2014 Charley enjoyed victory in Morocco at the Lalla Meryem Cup and then went on to finish 7th in her first ladies major of the year, The Kraft Nabisco Tournament. Charley finished 2014 by winning the LET Order of Merit and at the age of 18 is the youngest player to have had such an achievement.
Charley has represented Europe in the 2013, 2015 and 2017 Solheim Cups.
In March 2016 Charley was runner-up in the ANA Inspiration and in August represented Great Britain in the Olympic Games in Rio de Janeiro.
Charley secured her first victory on the LPGA Tour by winning the CME Group Tour Championship in 2016. Charley had a final bogey-free round of 66 to finish the week at 19-under par and set a new Tournament scoring record, previously set by Cristie Kerr at 17-under par in 2015.