Yes exactly. AGP and PCI slots are keyed to prevent users from fitting cards that are electrically incompatible with the _signalling_ voltage used by the system.
So you can't fit a 5V-only PCI card into a 3.3V-only slot. Just as well as you can't fit a 3.3V-only 1x/2x AGP card into an 1.5V-only 4x/8x AGP slot.
The difference is there are unkeyed, "universal" AGP slots, but no "universal" PCI slots. Cards may be "universal" on AGP and PCI. Yours is not 😉
Just for the record: What board is that? 3.3V-only PCI is rarely seen in the desktop world ...