Check in the # of opportunities. You will find they are not the same.
It's like this:
Guy goes all-in, you are closing the action. What are your possible actions?
Can you raise?
No. You can only call or fold.
So it logically follows that when you close the action, and it is an all-in to you, that there does not exist the opportunity to raise.
There will always be fewer opportunities to PFR than VPIP. But if you PFR, you VPIP'd by definition.
So you play 5 hands headsup in the BB vs an opponent.
In 4 hands, he min-raises, you can either call, raise, or fold. In 3 of these hands, you 3-bet in all 4.
In the 5th, he tires of being 3-bet, and shoves. You fold.
So in these, you have 5 opportunities to VPIP. You VPIP 4/5 (80%).
But you could only PFR 4 of them, in which you do PFR by 3-betting him. Your PFR and 3-bet would be 4/4, 100%.
If you check the popups, you'll see that there are different opportunities for the PFR than the VPIP, thus there are different denominators, they will not add to 100% and PFR can be higher than VPIP.