Villas-Boas paired Defoe with Emmanuel Adebayor from the start for the first time this season and the move worked well, with the duo combining well throughout.
Gareth Bale also played a big part in Defoe's excellent display, the Welshman providing the assists for the striker's first and last goals.
Villas-Boas showered praise on Defoe afterwards.
"He was amazing," the Spurs boss said. "It's important for him because he overtakes Teddy Sheringham's record in the club, which means a lot.
"It was good to see (Defoe play with Adebayor). It is important for us to have this option. It was good to see us use this system.
"He (Defoe) makes the most of the opportunities he gets.
"Gareth was amazing for him and when you have so much quality in the link-up you have the possibility to score and he's a good goalscorer."