It also left the 46-year-old Australian maestro expressing his delight at his form in the build-up to his 12th crack at trying to win Presidents Cup in Medinah, USA, next week.
Scott's day would have been even better on Thursday if he hadn't driven into the trees on the penultimate hole to drop his only shot before he went on to miss a short eagle putt on the last following a dazzling 200-yard approach at the par-five.
But the veteran was still well placed to launch a concerted bid to lift his first title in a four-round tournament since his Genesis Invitational win at Riviera on the PGA Tour in 2020.
The former Masters champion did win the two-round Cathedral Invitational in Victoria last year and in 2023, but, still ranked as high as 52 in the world, he's been frustrated at not being able to get across the line in PGA and European Tour events over the last few years.
"With the exception of 17, it was one of the best rounds I've played tee to green this year. So that's handy around Wentworth," smiled Scott, who recorded seven birdies and that lone bogey.
"It's a tough track if you're off the fairway, very hard to create opportunities. So I'm not going to say it was an easy 67, but it felt good."
If his five-footer for eagle hadn't slid by at the last, Scott would have joined England's PGA champion Aaron Rai and Sweden's Joakim Lagergren atop the first-day leaderboard after they both shot six-under 66s.
Scott was joined by American Ryan Gerard, Swede Ludvig Aberg and Spaniard Nacho Elvira in a four-way tie for second, while New Zealand's Open champion Ryan Fox was another shot behind in a 12-strong group on four-under, which also included Patrick Reed, Viktor Hovland and Robert MacIntyre .
Masters champ Rory McIlroy had been five under through 10 holes and in the outright lead, before some erratic driving proved costly coming home, as he made three bogeys over his final six holes to finish three-under.
Scott can't help but cast half an eye on next week's Presidents Cup, delighted to have qualified for the International team yet again after having tied back in 2003 and then lost the last 10 times to the dominant US team.
"The team's coming into great form," he noted. "It's a big week for us Internationals. It's always a hard task for us but it's going to happen, and it may as well be next week.
"It was one of my big goals this year to qualify automatically, so I'm pleased to have done that and not had to beg (captain) Geoff Ogilvy for a pick. Hopefully, I can get there and put some points on the board and we can get it done."
