However, the Ashes squad members were overshadowed by Matt Renshaw who did not make the cut with Australia's hierarchy opting for uncapped opener Jake Weatherald.
After Queensland were sent in, Renshaw made 101 off 198 balls and shared a second-wicket partnership of 103 with Labuschagne before WA fought back through quick Cameron Gannon late in the day.
"Obviously there's a bit of disappointment straight away but then you realise that it's not the end of the world," Renshaw said of being overlooked for the first Test squad. "It's a lot different to the way that I handled it eight-nine years ago. I just wanted to enjoy myself today and have intent."
Renshaw and Labuschagne had absorbing battles with Green, who claimed the opening wicket of Angus Lovell with a superb length delivery having entered the attack as the first-change bowler.
In a development that should please Australia's hierarchy, Green bowled two spells in the earlier part of the day to finish with 1 for 13 from 8 overs. He moved the ball dangerously when pitching up but also bent his back with several ferocious shorter deliveries.
Green consistently reached speeds of 135-140 kph in an impressive return to bowling after a side strain ruled him out of the India ODI series. He subsequently played as a specialist batter against South Australia.
Green's day was slightly soured after he had an uncharacteristic fumble in the gully to reprieve Michael Neser, who did fall moments later when Cooper Connolly took a spectacular catch diving backwards on the deep-third boundary.
"It's a different energy, there's just so much more on it," Gannon said of Green, who is unlikely to bowl on day two with the expectation that he will get through 15-20 overs across the match.
"It'll be really interesting to see him bowl at the [Perth] Stadium. I think he's going to do a great job. He's looking like he's got things pretty well under control at the moment."
Despite the warm weather and with little grass evident on the surface, WA captain Sam Whiteman continued the long trend of bowling first at the ground.
He looked set to rue the decision, with Renshaw in commanding form against the new ball with his best shot being an exquisite flick over deep midwicket that sailed into the vacant grass banks.
Renshaw was particularly dismissive of a wayward Matthew Kelly, who has been WA's standout quick to start the season. He continually used his wrists to whip on the leg side to make batting look far easier than in the two previous Shield matches on this ground.
WA needed a spark and Whiteman turned to Green in the 10th over. A bustling Green made an impact in his first over after unfurling a sharp delivery that whacked Renshaw on the left forearm. He threw his bat in agony and sought medical assistance but returned to batting and seemed unaffected despite sporting a notable bruise.
Green continued to menace and was rewarded by nicking off Lovell for 11 to set up an intriguing match-up with Labuschagne. His over-exuberance resulted in bowling a beamer first up, with Labuschagne somehow evading being hit but he did awkwardly fall on his backside.
Labuschagne was undaunted and pounced on a rare loose Green delivery to get off the mark in style. But the batters were tied down before lunch with speedster Brody Couch bowling a fiery spell in his first match of the domestic season having returned from injury.
Couch and his team-mates were adamant they had Labuschagne caught behind on 7 only to be left disappointed with a one-wicket opening session. Green bowled another four-over spell straight after lunch, testing Labuschagne with short-pitched bowling.
Labuschagne kept the runs ticking at the other end, continuing to take a liking to Kelly by stroking his best boundary of the innings with a gorgeous on-drive. He seemed set for the long haul after cruising to an 81-ball half-century having used superb footwork to dispatch offspinner Corey Rocchiccioli into the terraces.
But Labuschagne couldn't kick on after miscuing a short Aaron Hardie delivery to midwicket, leaving Renshaw to bat through the second session. He posted his second Shield century of the season just after tea before being caught behind attempting to hook Gannon.
Gannon turned the day on its head by clean bowling Jimmy Peirson on the next delivery to cap a stunning three-wicket burst. But Neser and Lachlan Hearne rallied with a 77-partnership partnership in a late twist.
Both teams boast near full-strength line-ups. Ashes reserve wicketkeeper Josh Inglis returns to red-ball cricket for the first time since the West Indies Test series, while quick Xavier Bartlett is making his Shield season debut having played in the white-ball series against India.