The King Richard star made his feelings known when Rock, who appeared as a presenter at the Academy Awards on Sunday, made a joke about Pinkett Smith.
"Jada, I love ya. G.I. Jane 2, can't wait to see it," Rock said during his bit, prompting Jada to roll her eyes at the joke. Moments later, after Rock quipped that that was "a nice [joke]" after being met with some uncomfortable reaction from the audience, he saw Smith make his way onto the stage.
Rock, who was chuckling, was then met with Smith's open-handed slap to his cheek. "Oh, wow," he immediately reacted, as Smith walked offstage.
The sound on the Oscars broadcast suddenly cut out after Rock said Smith's name in reaction. And as the camera panned back to the Oscar nominee, back at his seat, though there was no sound, you could clearly read what Smith shouted at Rock.
"Leave my wife's name out of your f**king mouth," Smith can be seen yelling back at the comedian.
Unsure how to proceed, Rock said, "That was the greatest night in the history of television," which was captured through ABC's telecast.
ET has learned that Denzel Washington and Tyler Perry had a private moment with Smith inside the theater during the commercial break following the altercation. The trio hugged and it appeared things had calmed down then.
"The theater was silent after Will got up and hit Chris. No one could tell if it was staged or a joke at first. Then Will started yelling at the top of his lungs and cursing out Chris. Chris was visibly shaken and the whole theater was dead silent," a source tells ET. "It was incredibly awkward for the whole audience. Will's friends and team have been trying to calm him down," another source tells ET.
Later in the evening, Smith won the Best Actor Oscar for King Richard and was visibly emotional as he took the stage to accept the honor. Though he did not directly apologize to Rock, Smith did offer an apology to the Academy.
At the end of his speech, Smith did add a dose of humor. "I'm hoping that the Academy invites me back," he said through tears as he let out a chuckle.
Rock's G.I. Jane joke may have hit a nerve for the couple, as Pinkett Smith has spoken publicly about having alopecia, a hair loss condition for which she was diagnosed with in 2018.
In late December, the actress shared an update with her struggles with alopecia, which is an autoimmune disease that also causes bald spots.
"Y'all know I've been struggling with alopecia and just all of a sudden one day, look at this line right here. Look at that," Pinkett Smith said on Red Table Talk, pointing to a line that showed up on her scalp as a result of the disorder. "So it just showed up like that and this is going to be a little bit more difficult for me to hide. So I thought I'd just share it so y'all are not asking any questions."
Rock has had a history of making jokes at the Smiths' expense. At the 2016 Academy Awards, which Rock hosted, Pinkett Smith was mocked by the comedian in his opening monologue. Rock skewered the actress, joking, "Jada said she's not coming. I was like, 'Isn't she on a TV show? Jada's gonna boycott the Oscars? Jada boycotting the Oscars is like me boycotting Rihanna's panties. I wasn't invited!'"
"Hey look it comes with the territory, we gotta keep it moving," Pinkett Smith told photographers as she walked through Los Angeles International Airport following the Oscars that year. "We got a lot of stuff we gotta handle, a lot of stuff going on in our world right now. We gotta keep it moving."