Two goals each from Frank Lampard and Steven Gerrard and one from Wayne Rooney avenged their heartbreaking 3-2 defeat by Croatia on a rainy night at Wembley 22 months ago, a result that cost them a place at Euro 2008.
England have qualified with 24 points from their eight games, with Croatia left in second place on 17 points with one match to play.
They are ahead of Ukraine on 15 points, who have two matches to play after drawing 0-0 with Belarus on Wednesday.
While the group winners qualify for the finals directly, the eight best second-placed teams from the nine European groups go through to two-legged play-offs for the four remaining places.
Fabio Capello's re-modelled side took control of the game from the start and never relinquished it.
Lampard scored with a seventh minute penalty and a 59th minute header while Gerrard scored with two excellent headers after 18 and 66 minutes.
Rooney added a fifth 13 minutes from time to put England into the finals with two matches to spare and send most of the 87,000 crowd inside the stadium wild with delight.
Croatia, without injured first choice keeper Stipe Pletikosa and playmaker Luka Modric, plus the suspended defender Vedran Corluka, were a shadow of the team that won at Wembley in 2007 and all they had to cheer was a consolation goal from Eduardo da Silva after 71 minutes.
EFFECTIVELY OVER
The match was effectively settled through Lampard's penalty and Gerrard's first well-directed header.
Aaron Lennon inspired England's glittering start, playing a significant part in both opening goals.
His run into the Croatia box was halted by Josip Simunic for the penalty. He then provided the perfect cross for Gerrard's header 11 minutes later and constantly bamboozled the Croatian defenders with his blistering pace.
England dominated the opening 45 minutes and could have scored five before the break.
Emile Heskey, preferred to the free-scoring Jermain Defoe, worked tirelessly linking attack and midfield but wasted two superb chances just before half-time.
England made light of those misses but despite their dominance they could not keep a clean sheet.
Robert Green, who hardly had a save to make in England's goal all match, was beaten when he parried two goalbound efforts but was powerless to stop Eduardo pouncing from close-range.
Rooney wrapped up the victory with his 25th England goal after keeper Vedran Runje miskicked a clearance giving him the simplest of opportunities to fire into an empty net.
