India started the match on a confident note, scoring two early goals to go 2-1 up at the breather at the University of Birmingham ground.
The visitors, however, failed to carry forward the momentum and conceded two goals in the second half to lose the opening series of their four-nation European tour.
Vikram Pillay (3rd) and SV Sunil (18th) scored for India, while England's marksmen were Ashley Jackson (30th, 50th) and Ian Mackay (64th).
England had earlier won the first Test 3-1 after which India came back strongly to level the series with a 4-3 victory in the second match on Friday.
The hosts, however, started the proceedings on a disastrous note with defenders Richard Mantell and Ali Wilson gifting India easy possession inside the opening two minutes.
The Indians started to put pressure on the rival defence from the very beginning and soon their efforts bore fruit.
A foul inside the circle following English custodian Nick Brothers' penalty corner save resulted in a penalty stroke in favour of the visitors and Vikram made no mistake in slotting the ball home.
With a goal lead in the early stages of the match, the Indians went on attacking mode and almost doubled their lead but for Brothers who made a good save off Dhananjay Mahadik's shot from the top of the circle.
India soon doubled their lead after a good interplay in the last quarter of the pitch between Rajpal Singh and Sunil, who smashed home from five metres.
Thereafter, England enjoyed a spell of prolonged possession but their probing was only rewarded with a number of long corners as India defended well in numbers.
In the 24th minute, Jackson's penalty corner effort was touched over the bar by Indian goalkeeper Adrian D'Souza.
However, Jackson found his spot just six minutes later when he unleashed a powerful drag flick high into the left corner of the Indian net to reduce the deficit before the breather.
The break in play seemed to have worked in England's favour as they came out all guns blazing after the change of ends and started to exert their authority.
England's persistent efforts finally resulted in a goal in the 50th minute when Jackson registered his second of the match with a powerful drag-flick from a penalty corner that beat D'Souza all ends up to level the scores at 2-2.
From there on both the sides played cautiously and seemed in no mood to give an inch to their opponents, but it was the hosts who had the final laugh when Mackay scored the winner from close range just six minutes from the hooter.
Starting the move, Rob Moore drove hard down the left of the midfield before switching play quickly to the right where an onrushing Richard Alexander fired the ball into the circle on the angle, and Mackay did the rest, deflecting the ball with pace into the net.
India, however, had a final chance of drawing the match when they were awarded a penalty corner with just 14 seconds remaining, but the English defence stood firm to thwart Arjun Hallapa's shot.
India will now head to Belgium for the second phase of their European tour which starts on Tuesday with the first Test match against Belgium.