Vasundhara Raje studied at Sophia College, Bombay, where she earned a BA (Hons) in Economics and Political Science. In 1972 she married Hemant Singh, the 7th Maharaja of Dholpur, Rajasthan. They have one son, born in 1973.
She began her political career as Vice President of the Yuva Morcha, Bharatiya Janata Party, in Rajasthan. Like her mother, she has remained in the BJP, while her brother has been in the Congress Party. She first entered politics in 1984, when she contested the Bhind seat in her home state of MP, but lost. The next year she shifted her campaign to Dholpur, her husband's home base, and was elected to the Rajasthan Lok Sabha where she served from 1984-89. She was re-elected to the Lok Sabha in 1989, 1991, 1996, 1998 and 1999. She was Union Minister of State for External Affairs in 1998. She served as the Minister of State for Small Scale Industries and Agro and Rural Industries, a new position created in 1999.
In November 2003, she resigned her cabinet post to run as BJP candidate for Chief Minister of Rajasthan. Although initial polls showed her running behind incumbent Chief Minister Ashok Gehlot, she won to become Rajasthan's first woman CM.