There is a gland in the anus that holds the spray for when it is needed. The spray is not pee. It is a special oily concoction that is made for the express purpose of deterring preditors.
Actually, there are two glands. One on each side of the anus. They are supported by a strong muscle which allows the skunk to spray up to 15 feet. The spray doesn't actually come from the anus.
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