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In English "an" is required before words beginning with a VOWEL SOUND regardless of how they are spelled. For example, "Please give me an M & M candy." Since the letter "m" is pronounced "em," the article "an" must be used before it. Usually, but not always, words following "an" begin with a vowel. On the other hand, they always begin with a vowel sound. It might be easier to remember to listen to the beginning sound of a word than to remember all the exceptions to the rule of using "an" before vowel letters.
If your question means does "a" or "an" come before the names of the letters, the answer is the same as above. Listen to the beginning sound of the letter name.
Examples:
an A
a B
an H
a P
an S
a U