Oscar-winning actor and humanitarian George had been chatting to CNN while attending a UN conference on Tuesday (20 September), when the reporter asked for his thoughts on the Brangelina divorce bombshell.
The what now, asked a clearly surprised George?
The reporter clarified that Angelina had filed for divorce from Brad, prompting George to say: "I didn't know that. I feel very sorry then. That's a sad story and unfortunate for a family. It's an unfortunate story about a family.
"I feel very sorry to hear that. This is the first I've heard of it."
Watch George find out about Brangelina's split below:
George is known to be very good friends with Brad: they starred together in the Ocean's Eleven trilogy and the drama Burn After Reading.
Angelina, 41, shocked the showbiz world when she filed divorce papers to end her two-year marriage to Brad Pitt, 52.
The papers were filed on 19 September and cite irreconcilable differences as the reason. It's been claimed she's seeking full custody of the couple's six children, with Brad having visitation rights.
Of course, this being a high profile Hollywood divorce, there are already numerous rumours floating around about what may have caused the marriage to breakdown but neither Angelina nor Brad has given an official reason.
Angelina's father Jon Voight said yesterday "something serious must have happened" for Angelina to end her relationship.
A statement released by Angelina's lawyer yesterday said: "This decision was made for the health of the family. She will not be commenting at this time, and asks that the family be given their privacy during this difficult time."
Brad later responded with his own brief statement, simply saying: "I am very saddened by this, but what matters most now is the well-being of our kids."
They share children Maddox, 15, Pax, 12, Zahara, 11, Shiloh, 10, and twins Vivienne and Knox, eight.
This is Angelina's third divorce following marriages to actors Johnny Lee Miller and Billy Bob Thornton, while Brad was famously wed to Friends actress Jennifer Aniston.
Brad was still married to Jen when he met Angelina while filming action comedy Mr and Mrs Smith, about a married couple who don't realise they're both assassins. There was huge speculation that Brangelina fell for each other on set, which seemed to be confirmed when Brad once commented their children could watch the movie where their parents fell in love.