Defoe, who has signed a three-and-a-half year deal, had been training with the youth development squad at Spurs since returning to England from Toronto FC during the MLS close season.
Striker Jozy Altidore moves back to the MLS, where he started his career, signing for Toronto as part of the deal.
Ten clubs reportedly wanted to sign the 32-year-old who opted for Sunderland, managed by his former Tottenham team mate Gus Poyet who was later assistant manager at Spurs while Defoe was a player there.
"I am thrilled that Jermain is a Sunderland player," Poyet told Sunderland's website.
"I know all about his attributes and his qualities first-hand and his exceptional goal-scoring record speaks for itself. He has something different, something special.
"We know each other very well - he was very young when we played together and I was coming to the end of my career, so I know him from inside the pitch."
On the day Defoe made his Spurs debut against Portsmouth in Feb. 2004, Poyet replaced him after 82 minutes.
Defoe scored the first goal in a 4-3 win over Portsmouth while Poyet scored the last-minute winner and the Uruguayan will hope Defoe has not lost his scoring touch as Sunderland seek to preserve their Premier League status this season.
They are 16th in the table, a point above the relegation zone.
Defoe has been one of the most prolific scorers in England over the last 15 years with 214 goals in 524 matches for Bournemouth, West Ham United, Portsmouth and over two spells at Tottenham.
Defoe scored a total of 143 goals for Spurs and is their fifth highest all-time scorer and their record scorer in European competition with 23.
He also netted 19 goals in 55 England appearances and in his brief spell in the MLS scored 12 in 17 games for Toronto.
(Reporting by Mike Collett; Editing by Ken Ferris and Justin Palmer)
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