A latecomer to the sport, Olivia Gollan only started competitive cycling when she was 26-years-old. She received a full scholarship with the Australian Institute of Sport in 2002 and won the Australian Road Championship in 2003 as well as silver in the Time Trial and finished the season ranked in the top ten in the world. Gollan made her Olympic debut, contesting the individual road race at the Athens 2004 Olympic Games. Gollan finished 12th out of 67 riders in a time of 3.25:42. After three years with the Australian National Team, she turned pro in 2005 with the German squad Equipe Nürnberger Versicherung, the number one team in the women's ranks at the time.