Set 299 for victory in Mohali, world champions India reached the target when captain Mahendra Singh Dhoni hit two consecutive boundaries off the first two deliveries in the last over.
Dhoni (31-ball 35) kept his calm and with Ravindra Jadeja added 65 runs for the unbroken sixth wicket to see India home.
A 111-run stand for the second wicket between Ajinkya Rahane (91) and Gautam Gambhir (58) kept the hosts close to the required scoring rate.
England came back strongly after Gambhir's departure and picked up four wickets in quick time with some inspired seam bowling but made crucial errors on the field in the closing stages.
Earlier, Jonathan Trott anchored England with an unbeaten 116-ball 98, after captain Alastair Cook won the toss and decided to bat first.
Trott added 101 for the third wicket with Kevin Pietersen (61-ball 64) and another 103 for the unbroken fifth wicket with Samit Patel (43-ball 70) after opener Cook (3) departed early.
Pietersen played a fluent knock and hit nine boundaries to increase England's scoring rate and laid the platform for Patel's late assault.
Patel hit seven boundaries and two sixes as the visitors finished with a flourish, scoring 91 in the last 10 overs.
The last two ODIs will be played in Mumbai (October 23) and Kolkata (October 25).
