She completed her school education from Presentation Convent, Kodaikanal, Tamil Nadu, and later graduated with Economics and Political Science degrees (Hons.) from Sophia College, affiliated to Mumbai University, Mumbai.
On 17 November 1972, Rana Hemant Singh married Maharajkumari Shrimant Vasundhara Raje Sahib Scindia (8 March 1953-), the third daughter of George Jivajirao Scindia of Gwalior and Rajmata Vijayraje Scindia.