'I have been rooting for a good round for a while,' said Stupples. 'It really felt good coming in here. I always feel like I should play well here in Corning.'
Stupples jumped out of the gate with birdies on each of the first two holes at Corning Country Club. She two-putted for birdie at the par-5 fifth and knocked a 7-iron to 10 feet for a birdie at the par-3 seventh.
At the par-4 eighth, Stupples dropped her approach within inches of the cup and tapped in for her fifth birdie on the front nine.
Stupples continued her fine play on the back half with a birdie at the 12th. She drained a 20-foot putt for a birdie at the 13th and made it three in a row when her third shot landed four feet from the cup at the par-5 14th.
Stupples, who was disqualified from this event last year for missing her tee time, parred the remaining holes to match her career low.
'The weather was fantastic,' said Stupples. 'You had a perfect lie if you were on the fairway all the time, which always helps your scoring. The greens were rolling very nicely today. I think over the course of the week, they slowly speed them up. In general, I thought it played very well today.'
The 29-year-old had plenty of support for the top player on the LPGA, who is competing alongside the men at the Colonial.
'I'm rooting for Annika 110 percent. I don't think anybody here in Corning is not rooting for her,' said Stupples. 'I was so happy to see that she's playing fantastic.'
Jones, a two-time champion of this event, collected three birdies on the front nine to make the turn at minus-3. She stumbled with a bogey at the par-4 13th but countered with a remarkable run down the stretch.
She birdied the par-5 14th and hit a 9-iron to 11 feet for a birdie at the very next hole.
Jones then birdied the 16th and picked up her fourth consecutive birdie with an eight-foot putt at the par-4 17th.
'I know all the holes after the 13th are birdiable,' said Jones. 'I think those holes are kind of an easy stretch right there, and if you get it down the middle of the fairway, you should be able to have a pretty good chance of birdie.'
Natalie Gulbis, Lorie Kane, Dottie Pepper, Mi Hyun Kim, Meg Mallon and Amy Fruhwirth finished in fifth at 5-under-par 67.
Denise Killeen, Juli Inkster, Nancy Scranton, Shani Waugh, Catriona Matthew, Pamela Kerrigan, Eva Dahllof and Marilyn Lovander were one shot further back at 4-under-par 68.
Defending champion Laura Diaz played the back side first and got off to a solid start with a pair of birdies over her first nine holes. Diaz found trouble around the turn, however, with four bogeys and two birdies to finish eight shots off the lead at even-par 72.