The primer. Rimfires use a priming material poured into the cartridge casing and allowed to harden. Rimfire cartridges can only be used once. Centerfire cartridges use a removeable disc shaped primer and can be reloaded after being fired. Centerfire cartridges are generally more powerful as well.
And the price of ammo to feed them. I just picked up a S&W M17 with a 4" brl in .22lr. Basically it feels like holding onto a 586 in .357 mag. Now I need the 586 I sold to a friend back so I have a "matched" set.
After all these technical explanations you guys forgot to answer the question. A rimfire pistol is so called because it's chambered for a rimfire cartridge, a center fire pistol because it's chambered for a centerfire cartridge.
(Sorry, just couldn't resist. Phase of the moon or something.)
Another thing, rimfire firearms - the firing pin strikes
the edge of the rim - dry firing is not recommended because
without a cartridge in the chamber it could result in
metal to metal contact and resulting damage.
Centerfire firearms, depending on the action, can
usually be dry fired but some may require the use
of Snap Caps. A Snap Cap is an inert or 'dummy:
cartrdge with a hard rubber insert in place of the primer
a case and seated bullet but no powder.
Dry Firing - pulling trigger in practice with no live ammo
loaded in the firearm.
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