Chasing 220 to win in 47 overs, India took a consolation win with three balls to spare, Mithali finishing undefeated at 75 of 86 balls.
It was India’s first victory on the tour. They pulled the single test before losing the first two ODIs.
Mithali beat slowly at first, but accelerated as the match progressed. She was well supported by number seven Sneh Rana, who produced a timely 24-race cameo for a 50-race partnership with her captain.
Opener Smriti Mandhana played a smooth 49-point shot to keep India in the chase.
This was after the Indian spinners took wickets at regular intervals to undo a promising start for England, who regrouped for 219 in the contest which became a 47-tag affair.
Captain @ M_Raj03 leads forward with a 7⃣5⃣ * winning game! 👏 # TeamIndia beat England by 4 wickets in the… https://t.co/tfE2xfc8vy
– BCCI Women (@BCCIWomen) 162533696000
Confident 49 from Natalie Sciver and 46 from Heather Knight backed up England’s heats while Deepti Sharma (3/47) took three wickets for India.
The two teams will now face each other in a three-game T20 series, which begins on July 9 at Northampton.
Shafali Verma (19) threw his wicket after another good start. Jemimah Rodrigues had impressive defensive technique but his poor swing rotation didn’t do the tourists any good. She consumed 21 balls for her 4 races.
Mandhana, on the other hand, not only kept a tight end but also performed some jaw-dropping offside workouts. Her steady head approach, her front foot hitting the ball field, and her bat connecting beautifully with her, made for a nice sight.
Her splendid blow ended when leg spinner Sarah Glenn trapped her in front of the wicket.
Mitahli and Harmanpreet Kaur (16) both hit slowly and this resulted in a required run rate of over six by over. Harmanpreet was fired when she missed a reverse sweep from Knight.
Television reruns showed that had she reviewed the appeal, the decision would have been overturned.
India demanded 14 of the last 12 balls, but Rana was dismissed in the last ball of the penultimate by Sophie Ecclestone.
Mithali however held his nerves to lead India past the finish line.
Previously, England were placed comfortably at 110-for-two, but their strategy of attacking Indian spinners resulted in the wickets falling into the clutches, resulting in a mid-order collapse.
Sneh Rana (1/31), Poonam Yadav (1/43) and Harmanpreet Kaur (1/24) each had a batter.
Sophia Dunkley (28) and Kate Cross (16 not eliminated) brought some useful cameos for England.
Indian had early success when Shikha Pandey trapped opener Tammy Beaumont (0) in the front leg. The positive intention of the home hitters meant that the Indians once again had to work hard without much success initially.
Knight and fit Lauren Windfield-Hill stroked, led and pushed the Indian bowlers with ease to keep a decent stroke pace.
Knight used the sweeping stroke effectively while Windfield-Hill used his feet well to charge the wicket.
Leg spinner Yadav drew in hitters with her steal and full deliveries, but didn’t pose much danger.
Sneh, who played a better length, broke the 67-point stand when Winfield-Hill swept but ended up battling Shikha Pandey in the middle of the wicket.
Sciver played freely, driving the balls with exquisite timing. His 49 came out of 59 balls with five limits.
Amy Jones (17) was unable to convert her strong start, however, and was dismissed by Deepti, looking for a big shot.
Sciver was denied the 50s by Smriti Mandhana, who pulled off a superb deep dive catch when the Briton tackled Deepti.
Knight was closing in on his first fifty in the series, but his sweeping shot at Harmanpreet landed straight into Pandey’s hands in the long run.
The Indian voltigeurs were lively and agile as they refused a few points to their opponents.