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The smallest, best known centerfire handgun round is the .25 caliber (or 6.35mm). The practicality of the .25cal is questionable: you have all of the costs of a centerfire round, with not much more energy than a .22LR rimfire. In fact, nowadays, you are much more likely to find .22LR pistols than a .25cal. One step up from the .25cal is the .32 caliber. This is just about as out-dated as the .25cal, but there were some very popular weapons in .32 caliber, the Walther PPK (James Bond's weapon of choice) is said to be a .32cal (not a .380ACP). There are also pistols made to shoot rifle (long gun) rounds. These tend to be smaller caliber than a .25 cal, but are fairly modern (like a pistol designed to fire .17cal HMR).