Any anime with Kensuke Ushio as the composer, most notably Silent Voice and Liz and the Blue Bird with prepared piano. He also composed the soundtrack for Dandadan and Devil May Cry
That's a pretty difficult question without examples or some details on what you're looking or.
Do song covers in non-music anime count as unique? Soundtrack for The Rolling Girls contains covers of The Blue Hearts (including Stones with a great Shamisen solo).
Girls Last Tour has Song of Raindrops as an ED to one of its episodes - it consists of vocals, soft beat and sounds of dropping water.
The original "Mobile Suit Gundam" trilogy (79 up to ZZ), "SDF Macross" and "Macross: DYRL" come to mind. It only makes sense, since a good space opera requires epic soundtrack. And those are the really big ones. Evangelion also has a very nice opening theme.