Hermes was the son of Maia by Zeus, leader of the Olympians. Little is sung or said about Maia in the songs and poems of the time, so we dont really know if he had any full brothers and sisters, from the union of Zeus and Maia. One thing we know about Zeus is that he was not a faithful husband to his principal wife Hera and Maia was his mistress. He had other mistresses, and with them reputedly had many children, much to the irritation of Hera. This makes Hermes an only child, a "love-child" of Zeus and Maia. It also makes him a half-brother to many of the Olympians, Ares, Apollo, Hephaestus, Athena being perhaps the best known of these. if you want to know more about how this family may have interacted, I suggest you read "Hermes the Olympian" a book written about them available on Amazon as an e-book and paperback.
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