Let's discuss unique books. What is the first one that comes to your mind? The uniqueness can be about the book's plot, structure, ideas, themes, topics etc.
For me such a book is Cat's Cradle by Kurt Vonnegut Jr. It's been a while since I've read it but I remember how mindblowing it was for me. Every time I thought it couldn't surprise me more, it actually did. There's a bit of everything there: peculiar characters, a substance called ice-nine that can freeze water on contact (as humans are around 60% water, it can instantly kill them), a fictional religion called Bokononism based on the idea that human life has no absolute truth or meaning, a tiny island nation with its own bizarre world. All of these come together to show us a satire of the absurdity of humanity.
As for a unique book structure, I have to say it's Cain's Jawbone by Edward Mathers. It's a kind of puzzle book where pages are not in order and you need to arrange them in order to guess whodunnit. I haven't finished this one yet but it's a cool challenge.
House or Leaves for the reasons already mentioned by others.
City of Saints and Madmen by Jeff VanderMeer. It's not exactly a story but a collection of artifacts: some short stories, poems, comics, an encyclopedia full of footnotes etc. that come together to build a world. Some of it is hard to read but the end result is worth it.
Changing Planes by Ursula K. Le Guin. Again a collection instead of a story. In each chapter a different world is described with its people and culture. And Le Guin is great at building worlds. I found this format very relaxing to read.
Discworld series by Terry Pratchett. I haven't read all books (there's too many of them) but if you like satire through fiction you'll find a lot of it here on a variety of topics.
And I think I'll stop here before this becomes a huge list.