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Here are some that have not already been mentioned
The Stars My Destination by Alfred Bester - considered by many to be the finest SF book ever written. Ostensibly about teleportation, it also touches on such minor topics as revenge, betrayal, love, hate, class warfare, and transcendence.
Rite Of Passage by Alexi Panshin - Nebula award winning novel. A fast, enjoyable read.
Lord Valentine's Castle by Robert Silverberg - First in a trilogy. The other two books, The Majipoor Chronicles and Valentine Pontifex, are also good, if not quite up to the quality of the first book.
There Will Be Time by Poul Anderson - an intriguing time-travel story.
The Man In The Tree by Damon Knight - the story of a pituitary giant who has other talents besides sheer size. Knight's novella "Natural State" is also worth a read.
Babel-17 by Samuel Delaney - the plot itself is just OK, but the characters that populate the book are what makes it special.
Voyage From Yesteryear by James Hogan - a story about Earth's first colony in the Alpha Centauri system.
Fun books
The Practice Effect by David Brin - explores what happens when one of the fundamental laws of physics works differently.
The Flying Sorcerers by Larry Niven and David Gerrod - the title might make you think fantasy, but this one is SF.
Dimension Of Miracles by Robert Scheckley - something like Adams's Hitchhiker's Guide, but better.
Glory Road by Robert Heinlein - swords and sorcery in the hands of an SF grandmaster.
Other authors I didn't see mentioned
Keith Laumer: The Retief books/collections are outstanding. Mostly short stories, but Retief's War and Retief's Ransom are two novel-length books I return to every now and then. If you like the Retief stuff you might also like Poul Anderson's stories about Ensign Flandry.
Gordon Dickson: The Alien Way - a well-constructed first-contact story. Dickson wrote a lot of good military-themed short stories, as well.
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