"I am excited for the opportunity and I've got the experience from leading in Ireland and other events that I've been in," she said. "I'm just going to try and use that - I'm feeling good."
A fourth birdie in her first 10 holes briefly extended Woad's advantage to three shots and, despite picking up further shots at the 14th and 17th, a bogey at the short 15th - only her second in 54 holes - left her 17 under.
That was two better than Denmark's Nanna Koerstz Madsen and South Korean Sei Young Kim, who shot an impressive 66.
Seven-time LPGA winner Hyo Joo Kim matched that to sit one back, while world number one Nelly Korda is five shots adrift on 12 under after a bogey-free 70.
The last time a player won on their professional Ladies European Tour debut was Singapore's Shannon Tan at the 2024 Magical Kenya Ladies Open.
"There was a lot of attention kind of leading up, so this feels a bit more free now that I've got my [LPGA] card," Woad said.
"I don't think you can ever expect to be leading, but I knew my game was good and I was playing well the last month or so. I definitely hoped to be contending. I'm where I wanted to be."