She told Star magazine: "I always wondered why they were attracted to each other. Here she is, this stunning woman. The two of them are total opposites. I thought it was baffling.
"Maybe it was their creative minds or intelligence. He is very charismatic.
"I heard through the family that Angelina was a very kind person and a wonderful humanitarian.
"The family never said anything negative about her. I think the biggest bond in his life is theirs."
With Jolie, 36, set to pen the foreword for Billy Bob's autobiography, deBin-Parish admits her own relationship with her former husband isn't quite so friendly.
She claims he refuses to communicate with their 32-year-old daughter Amanda Brumfield, who is serving 20 years in a Florida prison for aggravated manslaughter of a child.
- Bang! Showbiz