Salye, a St. Petersburg politician since the early 1990s, was a former chairman of the Free Democratic Party of Russia and a member of unregistered opposition party Parnas. She was also a People's Deputy from 1990 to September 1993 and participated in the Constitutional Council that created the nation's constitution.
Salye was a Putin critic since his time working at St. Petersburg City Hall. In 1992 she headed a commission created by the St. Petersburg City Council to investigate his activities as chairman of the Committee on Foreign Relations, which resulted in the adoption of a resolution calling for mayor Anatoly Sobchak to fire Putin and to instruct prosecutors to investigate suspected corruption and embezzlement. Sobchak ignored the recommendations.
Before her entry into politics in the late 1980s, Salye worked as a geologist.