The veteran actor, who co-starred with the Oscar-winning actress in the comedy Miss Congeniality, has revealed that James is "in a terrible emotional state".
Bullock announced her plans to divorce James and raise the couple's newly-adopted son Louis by herself after the revelation of her husband's 11-month affair came to light.
Speaking to The Insider, Shatner said: "My heart goes out to Sandra, who I know and love. My heart goes out to Jesse. I was at their wedding. I know he loved her. That marriage, that wedding was just beautiful.
"Jesse's being tormented like a matador with a bull. The paparazzi have nothing to lose so they are constantly waving the red flags. He's in a terrible emotional state. His whole life has been turned upside down. He doesn't know what he's doing right now."
