Charlesworth was coached by Ray House at Christ Church Grammar School, where he was promoted to the school's first XI at an early age. He was a member of the PSA Hockey Cup (now known as the Ray House Hockey Cup) winning teams of 1966–67.
In 1969 he captained the Western Australian State under 19 cricket team before going on to play A grade Club cricket for West Perth (1969–1970, 1976–82) and University Cricket Club (1970–76). He played in 47 first-class matches for Western Australia from 1972 until 1979, making 2,327 runs at an average of 30.22. He was a member of Sheffield Shield winning teams in 1972–73, 1976–77, 1977–78, and was a squad member in the winning season of 1974–75.
He played in and captained the Western Australia hockey team and the Australia men's field hockey team the Kookaburras. He was selected to represent Australia in five Olympic hockey teams, 1972, 1976, 1980 (captain) (Moscow Olympics were boycotted), 1984 (captain), and 1988, winning Silver at the 1976, Montreal Olympic Games. He was a member of the national team which competed in various other international tournaments including winning the World Hockey Cup in London in 1986 where he was named player of the Tournament. He retired from playing after representing Australia at the 1988 Olympics in Seoul. He played 227 games for his country and scored 85 goals.
In 1980, while playing for The University of Western Australia Hockey Club, Charlesworth also won the Olympian's Medal, an annual award presented to the player judged by umpires to be the fairest and best in men's first division competition in Western Australia. In addition, the female equivalent of this award, the Charlesworth Medal, is named in his honour.
He was elected as the Federal Member for Perth in 1983, representing the Australian Labor Party, and was a Member of Parliament for 10 years until retiring in 1993.
From 1993 to 2000 he was head coach of the Australian Women's hockey team, the Hockeyroos. During this time they won the Champion's Trophy in 1993 (Amsterdam), 1995 (Mar del Plata), 1997 (Berlin) and 1999 (Brisbane), the World Hockey Cup in 1994 (Dublin) and 1998 (Netherlands) and were gold medallists in the Atlanta Olympics in 1996 and Sydney Olympics in 2000 and 1998 Commonwealth Games in Kuala Lumpur.
Charlesworth was inducted into the Australian Hockey Hall of Fame in 2008, the second person to achieve this award.
In 2009, Charlesworth was appointed coach of the Australian men's national hockey team, the Kookaburras. The team went on to win the 2009 Men's Hockey Champions Trophy in Melbourne, Australia; the 2010 Hockey World Cup in New Delhi, India; the 2010 Men's Hockey Champions Trophy in Mönchengladbach, Germany; the 2010 Commonwealth Games Men's Hockey Gold Medal in Delhi, India and the 2011 Men's Hockey Champions Trophy in Auckland. After coaching the Kookaburras to success at the 2014 Hockey World Cup in Netherlands, he resigned.
He has written three books: The Coach – Managing for Success, Staying at the Top and Shakespeare the Coach.