When is Civ 5 most enjoyable for you?

Definitely late game. I play on Prince(even though I win every time on Emperor) for the role-play aspect. So when late game roles around I like to play the global defender & fighting epic inter-continental wars, very fun.
 
Normally it's the midgame.

Occasionally, it's the late-game when there is an interesting superpower vs. superpower game happening.
 
#1. Exploring the land around me early-game, the awesome feeling when your scout finds that PERFECT city spot, like 6+ Marsh as Netherlands on the cost, and then you settle it. Watching your empire take root and grow into its land, connecting the borders and sealing yourself behind the mountains in an impregnable empire. Very satisfying.

#2. Industrial-Era and forwards warmongering. In SP this is kind of the sad, lonely "I already won" phase of the game, but in MP it's so fun to silently build your huge navy and dispatch submarines in preparation for a secret amphibious invasion against an unwitting opponent.
 
I, too, love the ancient/classical era when you explore and find ideal starting locations. I enjoy going for the early wonders too. The founding and spreading/enhancing of religion is also great fun for me. And I usually put Shaka and Atilla in my games, so I find it spices up the game expecting an early attack from one of the two.
I had to laugh at the comment about when the wife and kid is in bed, as I truly enjoy my playing time early in the morning when my wife and two very noisy grandchildren are fast asleep:lol:
 
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