The Tottenham striker lifted the 73,000 crowd by netting after only three minutes and added a second just after the hour mark.
Substitute Adam Johnson made sure of the points in the 83rd minute before Defoe completed his treble four minutes from time.
Manchester United ace Rooney helped to set up all four goals, and Defoe paid tribute to his strike partner after the game.
He said: "I'm delighted with the performance tonight, not just the goals but the way we played and pressed in the first half.
"Obviously when you play with a partner it takes a bit of time to gel but Wazza (Rooney) is a great player and technically gifted. Like I've said before, if I make the runs he'll find me and he did tonight.
"When I got the second he said 'keep going and you'll get the third' and it's always nice when you play with a partner and he wants you to get the hat-trick. It's good."
Despite the one-sided victory, Defoe, who expects to be fit for Tuesday's clash with Switzerland, had a word of praise for rookie goalkeeper Joe Hart.
"Especially in the second half (he played well), there was a one-on-one and he made a great save. He's been like that all season for his club," the striker told ITV1. "What a prospect he is."