The two friends were both nominated in the Best Actor in a Drama category for their roles in Moneyball and The Descendants respectively and were also up against Leonardo DiCaprio and Ryan Gosling.
But it was George who emerged victorious on the night.
In his acceptance speech, the 50-year-old star stopped the jokes to praise Brad, 48, for his work over the last year.
He said: "I wanted to say it's nice to see Brad, and it's nice to be able to tell him not just what wonderful work he's doing in two films this year. But what wonderful work he does in the rest of the world to the rest of the people."
George was accompanied to the Golden Globes - which were hosted by Ricky Gervais - by his girlfriend Stacy Kiebler, and the former wrestler sent pulses racing when she arrived in a figure-hugging floor-length red dress.
Check out some of the highlights from the Golden Globes:
- BANG! Showbiz