The team with the worst away record in the top flight pinched all three points at Selhurst Park to ruin Palace's best start to a Premier League season thanks to former England forward Defoe's persistence in the 80th minute.
As Defoe tried to pounce on a loose ball, Scott Dann, trying to shield it, made a mess of his attempted clearance, poking the ball past indecisive keeper Wayne Hennessy into the path of the Sunderland striker who muscled through to tap into an empty net.
The three points enabled Sunderland to move up to 18th with nine points, ahead of Bournemouth on goal difference and four in front of bottom club Aston Villa. Palace lie 10th with 19.
"He is a classy finisher," Sunderland manager Sam Allardyce said of Defoe. "If you want someone to chase down what looks like a lost cause, it's him. Defoe not giving up is why the goalkeeper and defender messed up."
"I got that little bit of luck that you need for the goal and I was just delighted," Defoe added on Sky Sports. "The lads put in the work during the international break and it paid off."
Palace, for all their second half pressure, missed the chance of a win which would have moved them to sixth in the table and came nearest to breaking the deadlock fleetingly when Bakary Sako's speculative left-foot strike flew just wide.
Sunderland, though, under new manager Allardyce, deserved only their second league win of the season defending stoutly and being enterprising on the counter attack.
They had earlier come closest to scoring when defender Younes Kaboul's header from a corner was cleared off the line by Yohan Cabaye.
Allardyce added: "Defensively we were sound, rarely troubled in front of the opposition goal. We frustrated the crowd, we frustrated Palace and then we came out with a fantastic win, our first away win of the season."
(This story corrects the points margin over Villa to four in the fourth paragraph)
(Writing by Ian Chadband; editing by Ken Ferris)
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