Scott squandered a handful of chances to clinch the title with his errant putting while Ormsby missed a routine four-footer on the second extra hole that would have given him the championship.
All the while, Chalmers kept scrambling away. The left-hander shot a flawless final round of eight-under-par 64 just to get into the playoff then kept his nerve to win the longest ever playoff in an Australasian PGA Tour event.
“That was just phenomenal. I’m worn out," the 41-year-old said.
"I hit it off line, but I don't panic. I did it all week and I did it sometimes today, but I have a short game that I hold in pretty decent regard."
Ormsby, who won his first professional title in India last year, sank a long birdie putt on the 18th to get into the playoff but was eliminated on the third extra hole after Scott and Chalmers both made birdies and he didn't.
Scott and Chalmers then proceeded to par the 430 metres (470 yards) hole three more times before Scott, who was brilliant off the tee but erratic on the green, three putted from inside 30 feet and Chalmers two-putted from twice as far to claim his 10th professional title.
"The story of the week — I didn’t make any putts," Scott said. "I had so many looks. When you have putts to win the tournament you have to make them."
Scott and Ormsby had started the final day in a three-way tie for the lead with Scott Strange and both shot final rounds of 71 to join Chalmers at the top of the leaderboard.
Chalmers made eight birdies in a flawless round that featured two monster putts in excess of 50 feet. The 2011 Australian PGA champion hit 16 greens in regulation and took only 26 putts.
Scott, defending the title he won last year at the Royal Pines Resort on Queensland's Gold Coast near where he was raised, birdied the par-5 15th to get back to 11-under.
The 2013 Masters champion played the par-5s in 15-under for the tournament but struggled with the flat stick, unable to birdie the last three holes in regulation and making just one birdie in the seven playoff trips down 18.
New Zealand's Michael Hendry closed with a 71 to finish fourth at nine-under, one stroke ahead of American Scott Stallings (71) and two clear of Boo Weekly (74) of the United States.
(Writing by Julian Linden; Editing by Patrick Johnston)
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