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Definitely the Hobbit followed by LOTR, as others have said. If you still have an interest in more, I would start with the 'Children of Hurin', because it's a finished work. Then the Silmarillion and the Unfinished Tales. The Histories of Middle Earth is for diehards only - if you don't enjoy the Silmarillion (some people don't as it reads like a history) then you won't enjoy multiple versions and revisions of those stories.
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