Defoe, who scored 19 goals in his 55 England appearances, last played for his country in November 2013 and has spoken of his hurt at being overlooked for last year's World Cup.
The 32-year-old signed for Sunderland from Toronto FC in January, heading back to England after 11 months with the MLS club with a view to re-entering international manager Roy Hodgson's plans.
He has now scored twice in three league appearances since his move.
Hodgson was at White Hart Lane on Saturday to see Tottenham Hotspur striker Harry Kane score twice in a 2-1 win against Arsenal and Poyet said former Spurs man Defoe could play alongside the uncapped Kane for England.
"When you pick strikers you pick those in form and scoring goals," said Poyet, who was a team mate to Defoe at Tottenham. "We saw today Harry Kane at Spurs and it's an obvious choice, but Jermain has a chance if Wayne Rooney plays in midfield.
"But that's up to Roy (Hodgson) to decide. I respect the manager of the national team and the only thing the player can do is perform.
"He (Defoe) is special and there are not many (like him)."
Sunderland are 14th in the league table but only four points above the relegation zone.
Poyet believes Defoe, who scored his first Sunderland goal in a 2-0 home win against Burnley last weekend, can propel the side up the table.
"Proven Premier League goalscorers cost a lot and to find one that can come to us is quite difficult so he's very important for us," Poyet explained.
"Now we know what he can do because he can score from nothing. He knows what he can do and gives us the confidence as a team that sooner or later he will put the ball in the back of the net.
"If we do our jobs, then if we find him on the pitch, then I'm sure he is going to score plenty and that will be a platform for the rest of the season."
(Reporting By Sam Holden, editing by Alan Baldwin)
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