Maiden one-day centuries for Alistair Cook and Ian Bell helped England to 288 for two first in overcast conditions in the day-night match.
India were always struggling after limping to 38-4 in 15 overs thanks to three wickets in four overs for James Anderson, who ended with career-best figures of four for 23 off 10, and were all out for 184.
The victory was built on one of England's best one-day batting displays for a long time after they were put in by Rahul Dravid.
After losing Matt Prior for 19 in the 11th over, England picked up the pace impressively through Cook and Bell.
Opener Cook, playing fluently in only his sixth one-dayer for England, reached his century off 122 balls before falling for 102 when he got an inside edge onto his stumps while swinging at RP Singh.
Bell, who reached a high-quality century off exactly 100 balls, was then joined by Kevin Pietersen, who chipped in with 33 off 25 balls in a steady but unspectacular unbeaten stand of 67, Bell ending on 126 not out.
India's chase started smartly until Saurav Ganguly earned the rare distinction of being run out by Monty Panesar, often a figure of fun in the field.
Anderson then took hold of the match in a lively spell that removed Gautem Gambhir, Sachin Tendulkar and Yuvraj Singh to leave India reeling.
Dravid and Mahendra Dhoni steadied the ship, but slowly, and their 68 in 18.4 overs left them well off the pace.
Dhoni then gloved a catch behind to give Andrew Flintoff a wicket to mark a fiery return to international action for the all-rounder after he missed the 1-0 test series loss to India with an ankle injury.
Flintoff, fast and accurate, took one for 12 off seven overs.
Dravid went for 46 in the next over, caught behind to give Dimitri Mascarenhas his first international wicket and impressive figures of one for 28 from his 10 overs of medium pace.
India then fell apart with some terrible running between the wickets that led to Ajit Agarkar and Piyush Chawla both being run out.
Anderson yorked Zaheer Khan while Panesar ended things by bowling RP Singh with the last ball of the 50th over, leaving Dinesh Karthick not out on 44.
The second match of the series takes place in Bristol on Friday.