He received his early education at the Ajmer Military School (formerly King George's Royal Indian Military School) in Ajmer, Rajasthan. He graduated with a master's degree in economics from the University of Agra in 1967, obtaining first position.

Doval joined the IPS in 1968 in the Kerala cadre. He was actively involved in anti-insurgency operations in Mizoram and Punjab. Doval was one of three negotiators who negotiated the release of passengers from IC-814 in Kandahar in 1999. Uniquely, he has the experience of being involved in the termination of all 15 hijackings of Indian Airlines aircraft from 1971–1999. In the Headquarters, he headed IB's operations wing for over a decade and was founder Chairman of the Multi Agency Centre (MAC), as well as of the Joint Task Force on Intelligence (JTFI).