Langer matched Bryant at 6-under 66 at The Woodlands Country Club. Langer won the 2007 event at Augusta Pines and successfully defended his title in 2008 at The Woodlands. The 56-year-old German player won the season-opening event in Hawaii for his 19th Champions Tour title and has 20 straight under-par rounds.
The birdie streak tied Dan Forsman's 2009 tournament record.
"You want to keep going," Langer said. "I was sad the day was over. I would've liked to try a few more holes to make a few more birdies."
Bryant won the Dick's Sporting Goods Open last year for his lone victory on the 50-and-over tour.
He rebounded from a bogey on the par-5 13th with three straight birdies.
"I felt like it was a real anomaly, but then to hit a really good iron shot and salvage the bogey was pretty big," he said. "That kept my spirits up."
"I just have to get used to the position where I'm at," Toledo said. "I'm not scared. I've played on the tour against Tiger in front of 50,000 people. Maybe more than that. I'm not afraid to lose. I might lose but I'm not afraid."
Toledo, who moved to The Woodlands after last year's tournament, said he is still in a whirlwind from that win.
"To be honest with you, I can't believe I see my pictures on those little badges," he said. "It's funny to me. I've never seen anything like that. It kind of got me going."
Woodlands resident Jeff Maggert, Fred Funk and Joe Daley shot 68. Maggert won in Mississippi in March in his first start on the 50-and-over tour. Funk won the 2012 event and the 1992 Houston Open on the course.
Fred Couples, the 2010 winner and a former University of Houston player, had a 69. He won in March in Newport Beach, Calif.