Greg Keyes "Age of Unreason" series : "Newton's Cannon, A Calculus of Angels, Empires of Unreason, and The Shadows of God" Don't judge Keyes by the Elder Scrolls novels, this series is intelligent, and sarcastically hilarious.
"The White Plague," and the "Dosadi Experiement" by Frank Herbert are also good sci-fi.
Hmm. Well, if your interested in a seriously long yet rewarding read, I'd recommend the Dark Tower series by Stephen King. It's his self-proclaimed magnus opus. While I couldn't classify it as "Science Fiction", it certainly has aspects of Sci-Fi in it, especially in the fifth book "Wolves of the Calla".
A Canticle for Leibowitz The Moon is a Harsh Mistress City of Illusions Planet of Exile Left Hand of Darkness The Dispossessed Stranger in a Strange Land The End of Eternity Foundation's Edge Dune The Stand Ender's Game Speaker for the Dead Hominids Humans Hybrids Wastelands: Stories of the Apocalypse Ringworld The Ringworld Engineers Slaughterhouse Five His Majesty's Dragon Yiddish Policeman's Union The City and the City