In 2006 at the age of 14 Whiley claimed her first senior main draw titles when she won the singles and doubles at the Cardiff Wheelchair Tennis tournament, also winning the girls title.[6][7] At the end of 2006 Whiley had moved up from 112 to 48 in the rankings and had won junior titles in Poland and the Netherlands.[8][9][10] Whiley won two awards at the British Wheelchair Tennis Association awards: Most improved female player and players' player of the year.[11] Whiley created history in 2007 when she defeated Katharine Kruger in Tarbes. She became the first Briton to claim the Cruyff Foundation Wheelchair Juniors Masters title, Whiley also claimed the doubles title with Louise Hunt.[12] Following on from the Masters success Whiley won her second senior title at the North West Challenge.[13] Whiley followed this up by becoming the youngest national British Champion and winning the doubles title as well.[11][14] Whiley then successfully defended her Cardiff wheelchair tennis tournament titles.[7] In 2008 Whiley successfully defended her Masters titles; defeating Emmy Kaiser in the singles before partnering Hunt to back to back doubles titles.[15] The following week Whiley claimed her first international title the Sion Indoor.[16] Whiley then successfully defended both titles at the North West Challenge.[17] She was named in the team for the 2008 Paralympic Games.[18]
Whiley and her partner Yui Kamiji of Japan achieved a calendar Grand Slam by winning the wheelchair doubles at the Australian Open (beating the Dutch pair Marjolein Buis and Jiske Griffioen), the French Open, Wimbledon and the US Open (overcoming Griffioen and fellow Dutchwoman Aniek van Koot in all three finals). They finished the year by adding the Masters crown after defeating Louise Hunt and Katharina Kruger in the final. However, despite the absence of van Koot and Griffioen the pair did not go undefeated throughout the tournament as they lost to Marjolein Buis and Michaela Spaanstra during the round robin group stage.[23]
Whiley and Kamiji are four times doubles champions at Wimbledon, and Whiley was 11 weeks pregnant when they won their 4th title, in 2017.[24][25] Whiley did not participate at the Championships in 2018, after giving birth to her son, earlier that year. She planned a comeback in late 2018.[26] In the 2020 season, she won the Australian Open and US Open doubles titles.