Adam Johnson weighed in with the other goal as Rooney's year-long international goal drought continued but it was a night of celebration for the Manchester United forward who had a hand in all four goals, starting with a deft lofted pass in the build-up to Defoe's third-minute opener.
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Rooney looked sharp and full of running in the Group G Euro 2010 qualifying win - a total contrast to the dejected, weary-looking figure he cut during the World Cup.
Manager Fabio Capello said a new, deeper role had been key to his new productive streak.
"I played Rooney in a position different than usual. He did very well. I spoke with him before the game," Capello said.
"He had to stay just in front of the two central midfielders and from this position to go forward and to be free. The quality of Rooney was really high."
Defoe was also full of praise for his provider-in-chief. "It's always nice when you play with a partner and they want you to score the third goal," Defoe said.
"When I was on the second, he said to me, 'keep going and you'll get the hat-trick' and when I did, he was the first one to come over."
Of the strike partnership Defoe said: "I've always said sometimes it takes time to get things working.
"In training, we played together all week and it's been very good and in the game he was involved in all my goals - so it was brilliant."
Defoe suffered a bruised foot in the act of scoring his third but though he was immediately substituted he is expected to be fit for Tuesday's awkward-looking trip to Switzerland.
The news looks grimmer for centre back Michael Dawson, who suffered knee ligament damage and who will probably find out later on Saturday the full extent of the problem that seems certain to rule him out for several weeks at least.
With regular centre-backs Rio Ferdinand and John Terry also injured England will field Phil Jagielka, who looked quick and efficient on Friday, alongside either Gary Cahill, who made his debut as Dawson's replacement, or Matthew Upson, one of the players most heavily criticised for his World Cup performances and left out of Friday's match squad.
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