Millipedes smell for the same reason that skunks smell. The emit a bunch of toxic chemicals such as cyanide when they are handled or threatened. This is a defense mechanism. The smell makes them an undesirable target for predators.
Millipedes are not poisonous, but many species have repugnatorial glands capable of producing irritating fluids, which may produce allergic reactions with people who are sensitive to insects or insect toxins. A few millipede species are capable of squirting these fluids over a distance of several inches. It is not recommended to handle millipedes for this reason, as the fluid may be dangerous to the eyes, and if you come in contact with a millipede, wash hands with soap and water until smell disappears.
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