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1. Freeport - EQ2
Nothing got my hooked in EQ2 as the evil and grandiose look of Freeport. Too bad SOE never managed to create the social tools/functions letting players actually spend some time there.
2. Bree - LotR
Not as good looking as Freeport, but few NPC cities have the same player activity as Bree in LotR. There are always people around in this charming medieval town.
3. Neriak - EQ1
As a long time dark elv necromancer, Neriak was the obvious choice of home. Returning back to Neriak through Nektulos Forest after several weeks of adventuring in far, distant lands always had a strong feeling of returing home. Neriak was one of few places where NPC guards would not attack me on sight; it was a safe haven for a necromancer.
4. Theed - Pre CU/NGE SWG
There was a time when Theed was crowded with players socialising, talking, spamming adds and killing each other in the constant feuds between rebels and the empire. Even though the city itself was very flatt and boring looking, the myriad of players created and interesting place to visit.
5. Yrkanis - Saga of Ryzom
As a former Matis inhabitant, Yrkanis was the crown jewel. Numerous hours have been spend by the stables chating with fellow inhabitants of Atys and admiring the organic and wood-like architecture of Matis. It was a beautiful city, somtimes filled with players, other times very empty and lonely.
So, this is my list of NPC cities, based upon nothing else than the feel of being in them. Now, give me yours!
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When in doubt, troll.