Abdessalam Benjelloun’s diving header proved to be just enough to deprive 10-man Saints of a point during their SPL curtain raiser at Easter Road.
Stevie Thomson saw red for a 15th minute challenge on Hibs midfielder Partick Cregg but Stephen McGinn opened the scoring with a fine drive after 38 minutes.
The lead was short-lived, though, as David Wotherspoon restored parity a minute later.
And Benjelloun came off the bench in the second half to score what proved to be the winner.
Andy Dorman sustained a head knock in the first couple of minutes when he tried to connect with a Jack Ross free-kick into the box but the midfielder returned to the fray after treatment.
Paul Hanlon saw an effort in the box blocked by the body of Ross after Cregg swept an inviting cross into the box, before Saints carved out a good chance of their own.
Nice build-up play saw Billy Mehmet force a save from Yves Ma-Kalambay after a Ross diagonal ball into the box found Michael Higdon and the former Falkirk striker found Garry Brady’s run.
Brady poked it into the path of Mehmet but Ma-Kalambay was well positioned to deal with his drive.
Minutes later, Mehmet headed over from around 12 yards as once again, Ross burst down the right after a pass from Dorman before delivering a great cross into the box.
Striker Higdon picked up a caution for a foul on Souleyman Bamba but there was even more controversy after 15 minutes when Thomson was instantly dismissed for a tackle on Cregg.
McGinn lost possession near the centre circle, tried to retrieve the loose ball but seconds later Thomson’s challenge on former Falkirk man Cregg gave referee Alan Muir a tough decision to make – and he flashed the red.
With only 10 men, Mehmet was forced to drop back nearer midfield to compensate.
Kevin McCann forced a Hibs corner on the left off the boot of Ross but Derek Riordan’s resultant cross zipped behind for a goal kick.
There was a scare for skipper John Potter when he picked up what looked like a slight groin strain towards the midway point after he hoofed clear a cross from the left.
However, the big defender seemed to shrug off the discomfort.
Higdon won a Saints free-kick 35 yards out on the left and it was a chance for the visitors to send it into the dangerzone, but Bamba managed to head flick it behind for a corner.
From Dorman’s cross, the Hibs rearguard cleared it.
Riordan won the home team a free-kick after he was impeded by David Barron five yards from the corner flag, but Hanlon’s header from 14 yards crept wide of the right hand post.
After 37 minutes, Colin Nish saw a great header from 12 yards zip marginally wide of the right hand post after Cregg played in the cross, before Saints took a dramatic lead a minute later.
Ma-Kalambay allowed a Chris Hogg passback to roll dangerously towards goal, before feeding Hanlon.
Dorman picked up the scraps and played in a cross for which Ma-Kalambay failed to hold.
Mehmet picked it up, teed up McGinn and the young Saints midfielder drove a lovely shot high into the net.
Less than a minute later, Hibs drew level when John Rankin won the ball, picked out Riordan, whose cross back in found Wotherspoon in the perfect position to divert it home.
Paul Gallacher easily saved a Riordan low angled drive after 44 minutes, before Nish headed Rankin’s cross inches wide of the right hand post.
After 50 minutes, Hibs were denied by the woodwork when Nish saw his header hit the underside of the bar.
Wotherspoon headed it on, following Cregg’s corner on the right, but from four yards Nish watched in agony as the ball failed to drop behind the line.
After 56 minutes, Bamba won the ball in midfield, charged forward and unleashed a deflected shot from distance – but Gallacher was there to take the catch.
Higdon saw a decent shout for a penalty turned down a minute later when Hogg clambered all over him in the box as they challenged for a high ball.
Rankin saw a fizzing effort from 22 yards drift just over the crossbar.
Tom Brighton replaced Higdon in St Mirren’s first change of the afternoon, after 72 minutes, before Gallacher was forced to parry away Rankin’s right foot drive from 22 yards.
Then McBride hit a superb shot from distance that Gallacher had to parry over and Benjelloun sent a first time effort wide of the far post when Riordan played him in.
But Hibs got the winning goal after 83 minutes when Riordan played a short corner to Daniel Galbraith and the youngster floated in a great cross for Benjelloun to head home from 12 yards.
Gallacher was called upon again to tip over Riordan’s angled shot from eight yards as the home side looked to extend the lead.
Late on, Brighton missed a great chance to equalise when he left Hogg for dead with a nutmeg but his shot deflected over for a corner.