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I love both of them. Civ V's recent expansion, Gods and Generals, added a lot of content to Civ V, including a slew of new civilizations and a religion system; before these additions were made Civ5 felt fairly incomplete when compared to Civ4 (which benefitted from multiple expansions). Now that Civ5 has begun to receive expansion content, it's really coming into it's own.

The biggest difference between the two, in my opinion, is the fact that in civ4, you can stack a hundred units in a single tile, whereas in civ 5, it's one unit per tile. One unit per tile makes your units feel like massive armies, and you need to put a lot more thought into deployments and maneuvers- in civ 4, you just move your infinitely large army (the Stack of Doom) from city to city. The AI in both games is not that great a general; in Civ4 the computer will never really develop effective means to stop your stack (ie massed artillery, bombers, or nukes); in Civ 5, the AI lacks the foresight of a human player and often fails to protect archers, artillery, etc. behind frontline troops.

I'd advise grabbing Civ 5, but if you do spring for Civ 4, you'll no doubt enjoy it.