Sykes scored 12 goals to become the second-highest scoring Golden Boot winner behind only teammate Michelle Heyman’s tally of 15 set five seasons ago, equalling Kyah Simon’s 12 goals in 2010/11.
The pacy Dubbo-raised forward scored an astonishing 11 goals in the past seven matches, to help Canberra win the Premiership with a league-high 33 goals.
Sykes went ahead of Sam Kerr in the final round, with the Perth Glory captain finishing with 10 goals.
Early pace-setter Natasha Dowie impressed with nine goals for bottom side Melbourne Victory, and the English striker was joined by the fast-finishing Adriana Jones on the final day of the season, with teammate Sofia Huerta a further goal adrift.
Sykes, capped 19 times by Australia, adds the accolade to a burgeoning resume which includes last year's Julie Dolan Medal as best player in the Westfield W-League.
2016/17 Westfield W-League goalscorers
Ashleigh Sykes (Canberra United)
Sam Kerr (Perth Glory)
Natasha Dowie (Melbourne Victory)
Adriana Jones (Adelaide United)
Sofia Huerta (Adelaide United)
Jess Fishlock (Melbourne City)
Tameka Butt (Brisbane Roar)
Rosie Sutton (Perth Glory)
Katie Stengel (Western Sydney Wanderers)
Remy Siemsen (Sydney FC)
Jenna Kingsley (Newcastle Jets)
Jen Hoy (Newcastle Jets)
Racheal Quigley (Adelaide United)
Nickoletta Flannery (Canberra United)
Vanessa DiBernardo (Perth Glory)
Katrina Gorry (Brisbane Roar)
Arin Gilliland (Newcastle Jets)
Kyah Simon (Sydney FC)
Leena Khamis (Sydney FC)
Steph Ochs (Canberra United)
Marianna Tabain (Melbourne City)
Grace Maher (Canberra United)