The jaw-dropping moment took place moments after Rock arrived on stage to present the award for Best Documentary Feature.
It all kicked off when Rock, 57, pointed to Smith, 53, and his wife, quipping: ‘Jada, I love ya. G.I. Jane 2, can’t wait to see it.’
The joke was in reference to the 1997 film G.I. Jane, a role that actress Demi Moore famously shaved her head for.
At that point, the camera turned to Smith, who at first was seen visibly laughing at the gag and even clapped his hands, a gesture that seemed to suggest he saw the funny side.
But as Smith laughed while still seated, Pinkett Smith – who has been open about her struggle with hair loss and alopecia – visibly rolled her eyes, looking furious.