The 40-year-old was unplayable as he knocked in breaks of 65, 91, 81, 105 and 59 as the world number one was forced to sit and watch for the majority of the contest.
Selby has had a quiet season but showed signs that he was returning to some form in his opening round win over Barry Hawkins, but few would have expected the level of performance he showed against the Rocket.
The world number one had won 16 consecutive matches before this outing, but barely got a look in against his old rival in a rare whitewash loss for the seven-time world champion.
‘To beat Ronnie in any tournament, any scoreline is a great victory,’ Selby said on ITV4. ‘To beat him in the way I did, the way I scored, safety was good, long game was good.
‘Very, very pleased. The back end of the game against Hawkins I felt like I’d got a bit of confidence. I was striking the ball a lot better, seeing the shots a lot better, being a bit more positive. I just managed to carry that on into today’s game.’
The match started off in bizarre fashion as early in the first frame O’Sullivan missed a red three times despite being able to fully see other reds.
That should be a loss of the frame, but the referee must warn the player after two misses and Desislava Bozhilova forgot to do so.
Without a good safety shot to play, O’Sullivan hammered a cluster of reds and hoped for the best, which was not forthcoming.
From there on in it was all Selby with a string of big breaks until a closer final frame, with Selby getting over the line in incredibly short order on the final black. The match lasted just one hour and 40 minutes in total.
Next up for Selby is a semi-final against either John Higgins or Zhang Anda who will play their quarter-final contest on Friday.
The other semi-final is already set between Ali Carter and Mark Allen after the Captain downed Judd Trump on Wednesday night and the Pistol beat Gary Wilson earlier on Thursday.
O’Sullivan had lost just three games all season before the heavy defeat at the hands of Selby, winning the Shanghai Masters, UK Championship, Masters and World Grand Prix along the way.
Selby joins the short list of Zhang Anda and Lyu Haotian who have bettered the Rocket this campaign, with Zhang managing it twice.
Somewhat surprisingly it is not that long since O’Sullivan was whitewashed, though, losing 5-0 to Tian Pengfei in last year’s Welsh Open.
MORE : Mark Selby fired up for Ronnie O’Sullivan showdown at Players Championship
MORE : Ronnie O’Sullivan is given far too much respect by opponents, says Stephen Hendry
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