James, a three-time winner on the Champions Tour, got his most recent victory at the 2007 Allianz Championship.
Dan Forsman, who joined the Champions Tour in July, was in second place after a 64. Keith Fergus was another stroke back with an opening 65.
Dave Stockton, who tied for seventh in this event last year, shot a 66 and shares fourth place with Walter Hall and Gene Jones.
"I've been playing better and better lately," James said. "The course fits me. I've had success here before. But I've never had six birdies in a row before. I almost ruined it with an eagle at 15."