Hampshire boasted the better of the first day despite being put in by Gary Ballance without a toss – with the total on 281-4 at stumps.
Not even the inclusion of England duo Joe Root and Jonny Bairstow could steal the limelight from the supreme Vince.
Vince enjoys facing Yorkshire. He scored his maiden first-class century against the county in 2010, before this one he score his most recent century and he has more centuries against them than anyone else.
Vince’s three figures which came in the over after tea, was his first since this week a year ago – when he scored 129 at Headingley against the White Rose to save a draw.
In front of the current England captain Joe Root this was Vince in full flow – driving beautifully and playing everything else with a deft touch.
In a way the innings was a redemption for the right hander after his frustrating summer in 2016 with the national side – where he managed 212 runs in 11 innings before he was ditched.
So when he brought up his three figures with a back foot punch through the covers after 180-deliveries it was apt it had come off Root’s bowling.
A skip and a jump as Vince ran between the wickets to celebrate his milestone unleashed him – and allowed him to become more expansive as the evening wore on.
Every wicket that fell, Vince was the man to make sure the continuity was there – which allowed big stands with all his partners.
Afterwards, when reflecting on the day’s play, Yorkshire captain Ballance admitted his team had endured a day of missed opportunities.
“We bowled quite well in the first two sessions,” said Ballance. “There were a few chances which went down which is not ideal.
“We let it get away from us in the last session. If we can get a few early wickets tomorrow we can put them under pressure.
“We knew it would be a good wicket but we thought with the overhead conditions it would swing around a bit. We bowled nicely and put them under pressure early on but couldn’t sustain it for the whole day.
“Ben bowled nicely again. I think he has three now and it is great he is staying hungry and backing up his performances.
“Vince played nicely he is obviously a very good player. It is a shame we put him down but he made us pay. Hopefully we can get him out early on tomorrow morning.”
Vince had been brought to the crease when Michael Carberry had chased Ben Coad, the precocious fast bowler, wide of the off stump to be caught behind in the sixth over.
Opener Jimmy Adams was more assured than his opening partner and played the anchor role for Vince.
The pair put on 66 for the second wicket before Adams became the 20th batsman to fall victim to Coad this summer as he was plumb lbw to the first ball after lunch.
Not to matter for Vince, as Tom Alsop arrived at the crease for his first County Championship innings of the summer.
Vince moved past fifty in 109-balls as the trademark flourishes started to appear – although he was lucky to be put down by Adam Lyth at third slip on 39.
Alsop appeared in fine form, after replacing the injured Rilee Rossouw in the side, but after a partnership of 82 with Vince he was pinned by Steven Patterson for 40 – the fast bowler’s 300th Championship wicket.
His stand with Sean Ervine, for the fourth wicket, was by far the most flowing as the duo collected runs at a speedy rate of 4.37 per over.
The Zimbabwean was another to look set before departing, this time after a 110-run partnership with Vince, as he became another to perish to Coad - caught behind to a good diving catch by Bairstow.
Liam Dawson bagged his 6,000th first class run in a short cameo at the crease before a second spell of bad light curtailed the day, with 11 overs lost.