Mitali Raj has played both Test and One Day International cricket for India's women's cricket team. She was named among the probables in the 1997 Women's Cricket World Cup when she was just 14 years old, but couldn't make it to the final squad. She made her One Day International debut in 1999 against Ireland at Milton Keynes and scored unbeaten innings of 114 runs. She made her Test debut in the 2001–02 season against South Africa at Lucknow. On 17 August 2002, age of 19, in her third Test, she broke Karen Rolton's record of world’s highest individual Test score of 209*, Mitali scoring a new high individual score of 214 against England in the second and final Test at County Ground, Taunton. The record has since been surpassed by Kiran Baluch of Pakistan who scored 242 against West Indies in March 2004.

At the 2013 Women's World Cup, Mithali Raj was No.1 Cricketer in the ODI rank among women. She scored her only one ton and 4 time half century in Test cricket, while she had score five time hundred and 40 time half century with best bowling of 3 wickets for 4 runs in ODI's. In February 2017, she became the second player to make 5,500 runs in Womens ODIs. Mithali Raj most matches captained player for India in ODI as well as T20I.

In July 2017, she became the first player to make 6,000 runs in Womens ODIs. She led the Indian team to the final of the 2017 Women's Cricket World Cup where the team lost to England by nine runs.