The Bournemouth striker, 36, even posed for photographs alongside reality TV duo Shelby Tribble and Clelia Theodorou.
Defoe has been training with Eddie Howe's squad this week, but the 36-year-old found time to his support his sister during the international break.
He rocked up to the opening of Stella Chase academy in a suave leather jacket and a black 'Icon' hat.
The 36-year-old smiled as he posed for a snap with his arms around Shelby and Clelia from The Only Way is Essex.
His sister and both of the reality stars celebrated with a glass of wine, but tee-total Defoe didn't.
The ex-England international star refrains from drinking alcohol to give himself the best chance of fulfilling his potential on the pitch.
Speaking about his decision to go tee-total, he said: "You do get more out of yourself if you don't drink."
But Defoe has struggled for form this season and he is without a goal after four appearances in the Premier League.
Joshua King and Callum Wilson have secured their spots in Bournemouth's starting XI, which has left the striker spectating from the sidelines.
Defoe will be hoping to break back into the team for Saturday's showdown with Southampton at Dean Court.
It was also revealed earlier this month he would like to become a manager when he finally decides to hang up his boots for good.
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