Her prior positions include Director of the Directorate of International Organizations and Human Rights (June 2001-February 2002); member of Parliament (1990-2001); and various diplomatic posts in Rome and San Marino (1975-1990). From 1991 to 1994, Poptodorova served as vice chairwoman of the Bulgarian delegation to the Inter-Parliamentary Union and as a member of the Coordinating Committee of Women Parliamentarians of the IPU, responsible for Eastern and Central Europe. From 1994 to 1997, she served as a member of the Bulgarian delegation to the Parliamentary Assembly of the Council of Europe.

Poptodorova holds degrees from the University of Sofia and the University of National and World Economy in Sofia.

She is married with one son.