The world No.7 was bogey free and missed just one green to post a six-under 65 to begin her Australian WPGA Championship campaign at the Gold Coast's Sanctuary Cove on Thursday.
The West Australian is hunting a third-straight title after claiming the Australian Open on Sunday - becoming the first homegrown winner in 12 years - and was a victor in Singapore two weeks earlier.
Green and England's Charlotte Heath shared the clubhouse lead all day before Kelsey Macdonald (seven-under 64) stormed home to create a one-shot buffer in a truly international field.
The Scot bogeyed her first hole but more than made up for that with 29 on the back nine, finishing with a birdie and then an eagle on the par-five 18th to jump the leading pair.
The $600,000 Australian WGPA Championship has only been contested once before and Green wants her name on the Karrie Webb Cup before setting her sights on an improved showing at the year's majors.
A winner at the 2019 Women's PGA Championship, Green has lamented a quieter majors showing in the years since.
"I haven't performed very well in major championships over the last few years," Green, who skipped the LPGA's $US3 million ($A4.3 million) Founders Cup to compete on the Gold Coast, said.
"The course is probably going to be a bit longer when we play major championships. That's something that you have to work on, is your ball-striking at those events.
"Having some solid stats this early in the season will take me really into a good run for the summer."
Green said she had been attempting to add more shape to her shots this year.
"Just feeling comfortable over hitting the ball right to left and also left to right, which is not really how I've always done it," she said.
"I've always tried to hit it kind of straight at targets, versus actually shaping my ball flight. So it's nice to obviously have some good results over the last couple of weeks, but also know where the ball is going."
Defending champion Su Oh, who won the inaugural addition at Royal Queensland in Brisbane four years ago, struggled on her way to an eight-over 79.
Playing partner and fellow LPGA talent Steph Kyriacou, who missed the cut at Adelaide's Open, again battled for a two-over 72 playing alongside Green in a rain-hit morning group.
Switzerland's Vanessa Knecht, Czech Lucie Vachova and Indonesia's Kristina Yoko were a shot back from Green at five under.
Australian amateur Jazy Roberts carded a three-under 68 while Hannah Reeves was the next-best local behind Green at four under, in a group that includes India's Diksha Dagar, Germany's Leonie Harm and Italian Alessandra Fanali.
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