Seriously, Spice and Wolf looks deceptively like a premise for an ecchi centric show but no! It's actually very educational. Teaching you about medieval economics and the culture of the time. It's amazing and the show's protagonists(Kraft Lawrence and Holo) are one of the best and most adorable couples I've seen. The way their relationship builds over the course of the series, it's... beautiful man. T^T
[sub]Also, season 3. I'm slightly bitter that there might be no season 3. >~>[/sub]
There's also:
Higurashi (for the craziness.
Hellsing and Hellsing Ultimate(the gore and Crispin Freeman's voice, come on)
Another (loved the premise, execution was slightly wobbly though)
Full Metal Alchemist (is it bad that I haven't watched Brotherhood? Probably. >.>)
Clannad (no tears were shed, but my heart was broken regardless.)
And that's it, I think... I'll update this list accordingly if and when I remember some more awesome anime.