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You can find out through trial and error. If your longsword of chaotic slaying +1 does nothing extra against them, they're likely not chaotic. Likewise, if the Protection from Good spell seems ineffective, it stands to reason they're not good.
Most creatures are one of the evil alignments (usually chaotic), but some like elementals and animals are true neutral. There are other exceptions too, but this is what you'll usually encounter.
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