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I'm not sure it would even be possible for me to limit my list to 100 books.
Suggestions that I don't think have been made yet (some of these depend on the sub-genre you prefer):
Piers Anthony's Xanth books. Punny and more Fantasy, but usually classed with SF.
David Drake's Belisarius series. (Military SF, but also has Alternate History basis, i.e. the military is horseback, swords, archers, etc.)
L Sprague deCamp's Lest Darkness Fall. Sort of like Mark Twain's Connecticut Yankee in King Arthur's Court (which I would also recommend although it's not usually classified as SF)
The Lost Fleet series (can't remember the author, but it's a pseudonym anyway. John Hemry, I think.)
And so many more that I can't remember offhand.
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