Punk has the longest reign of the last 25 years(1). Hogan's run from '84 to 88' was 1474 days, four days longer than Bob Backlund's second stint 1470, his first being 2135 (although WWE only recognise 648)(2). Then there's Bruno Sammartino with 2803 and 1237 and Pedro Morales with 1027(2).
Assuming Punk was working 3.5* matches a week he'll have done (434/7) X 3.5 = 217 matches in this reign.
I can't find anywhere to see what sort of schedule they worked before Raw started so I'm guessing:
Let's say Sammartino worked 2 matches a week: (2803 / 7) X 2 = 801 (round to the nearest whole match)
Even if he only worked 1 match a week during his reign it's 400.
Soooo, to answer your question: No. Odds are that Bruno Sammartino and possibly Buckland and Hogan will have had more matches during their reigns.
* Raw, 2 house shows weekly and a PPV once a month minus time off injured and any others he missed (I guessed)
Ps. I only did all this because I realised this will be my 600th post and a round number deserved some numbers. As a great man might say, "You're Welcome!"