Saints Alumni Media Call: LeCharles Bentley talks his O-Line Academy, Teammates, and MRSA

Brad01 said
I think he just always wanted to play for Cleveland, which is where he was from. Unfortunately for him he ended up suffering what would be a career ending injury on the first snap of training camp in his first season there.

But since he went there, their center Jeff Faine was available in a trade during the draft. So it worked out for the Saints anyway.
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Could be the case, according to Wikipedia he apparently he had a "verbal agreement" with Philly, although he could have been using them to leverage an offer from Cleveland.

Also it appears leaving the Saints didn't seem to have much to do with Payton, more disliking the entire organization. And since he was an FA, it was easy to bolt.