Breaks of 56 and 27 gave White, whose place at the tournament was only confirmed last week, the dream start against the world No 3.
O'Sullivan has won this title three times including last year with victory over Kyren Wilson while White's qualification came by virtue of triumph in the World Seniors Championship back in August.
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But it was the older player who looked more at home around the table at Coventry's Ricoh Arena as O'Sullivan was unable to sink a ball in the second frame.
Not long after he was three frames behind and staring down the barrel of a shock defeat, even a whitewash, while White had a golden opportunity to seal his first win over "The Rocket" in 14 years.
O'Sullivan was finally on the board with a break of 74 in the fourth frame but his cueing remained inconsistent and his long pot success was under 15 per cent.
White too missed opportunities, once in the fifth he got a massive kick on the black with a 38-point lead and then having compiled a break of 29 in the final frame and he rushed a red and threw his cue on the ground in disgust.
White appeared almost at the point of tears as he sat down to watch O'Sullivan race around the table in his signature style that had been missing from the match as a whole.
The five-time world champion made 76, his highest break of the match, to edge into tonight's quarter-final where he will face John Higgins or Stuart Bingham.
For White, he is left to wonder what might have been.
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