Anything Shinkai is gorgeous.

Other visually beautiful anime would be along the lines of Gankutsuou (the textures and environments, the characters themselves were awesome as well) and Howl's Moving Castle (mostly the scenery, like Howl's secret place or his room in the castle).

However, amazing animation plays a part as well, ie not just how the characters and sceneries look, but how they move and interact with the surroundings as well. Anime like Ergo Proxy and Samurai Champloo.

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["Character cannot be developed in ease and quiet"]