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Hmmmmm.....

Just off the top of my head right now...

Inherit the Stars, James P. Hogan (technically the start of a disjoint series, but wholly contained)
Code of the Lifemaker, also Hogan
Protector, Larry Niven (part of Known Space but a standalone)
Oath of Fealty, Niven & Pournelle
Left Hand of Darkness, Ursula LeGuin
The First Fifteen Lives of Harry August, Claire North
Job: A Comedy of Justice, Robert Heinlein

I'm actually surprised at how few books I've read recently were stand-alone works. Here's a few I liked from the last year or so.

The Priory of the Orange Tree is long enough it could have been two or three books, but it's all between one set of covers. It's epic, world-spanning stuff, a quest to save the world from a foretold evil and all that good stuff.

Sixteen Ways to Defend a Walled City has a much tighter time-frame. A seriously wry anti-hero, a mere mid-level officer in the imperial engineers, finds himself leading the defense of the capital. Like if the barbarians came to sack Rome and found a cowardly MacGyver in charge of the defenses.

And this one has a tendency to polarize, but I really liked it. The Raven Tower tells two converging stories. In the present, a warrior named Eolo tries to puzzle out the source of the turmoil in her nation. Long in the past, a separate narration follows a god (in the form of a rock) on a trail of revenge.

I think most of these are relatively recent;

The Priory of the Orange Tree bySamantha Shannon - I really liked this one.

The Gossamer Mage by Julie E. Czerneda - Didn't love, but a very different feel than other modern fantasy I've read.

Children of Time by Adrian Tchaikovsky - while there's another book in the world, this basically wraps up as a standalone.

Spinning Silver by Naomi Novik - for a fairy tale

Starless by Jacqueline Carey - I really liked, but it ends a bit fast since it is a standalone

Mem by Bethany C. Morrow - short, interesting concept

Blood of the Four by Christopher Golden

Space Opera by Catherynne M. Valente - wasn't my thing, but reminicint of Hitchhiker's Guide to the Galaxy

Just took a pic of my shelves and remembered this one:

Gnomon by Nick Harkaway

The Library at Mount Char, end of discussion.

Standalones with my reviews:

Station Eleven - /review/show...

Sea of Rust - /review/show...

A Calculated Life - /review/show...

Damnation Alley - /review/show...

Way Station - /review/show...

Slaughterhouse-Five - /review/show...

Fahrenheit 451 - /review/show...

The Handmaid's Tale - /review/show...

XOM-B - /review/show...

Brendan wrote: "The Library at Mount Char, end of discussion."

Brilliant book.

House of Suns is excellent SF

I second House of Suns! I adored it, a really brilliant novel.

If you want something heartwarming: The Long Way to a Small, Angry Planet is strictly speaking part 1 of a loosely connected series, but it wraps up and can be read as a satisfying standalone.

In fantasy, Sanderson has some beautiful standalone novels: I especially loved Elantris, but Warbreaker has nice unique ideas, as well.

Kindred is heart-breaking, beautiful time-travel SF in which a modern (black) woman is suddenly sucked into the Antebellum South - the kind of book one never forgets.

The Ocean at the End of the Lane is a really great modern fantasy/magical realism story with a child protagonist but not meant for children. I loved it!

If you want something literary with supernatural elements: The Luminaries (a mystery/ensemble cast/ghost story/love story set during the New Zealand gold rush which won the Booker Prize) and Amy Tan's The Hundred Secret Senses aren't marketed as fantasy, but that won't keep me from recommending them because I really enjoyed both books and they have strong supernatural/fantasy vibes.

If you'd like to just read something really short to get a feel for the author before committing to a long book or series: try one of the great "The Best Science Fiction and Fantasy of the Year" anthologies full of short stories and novellas. I love finding new authors through their short stories, and after one of those anthologies you'll have a good feel for a large number of SFF writers, you'll have read lots of finished stories, and you'll know which writers you might like to read more of. Volume 11 is currently on sale for 0.99 USD:

I'd also like to thank everyone else for their recommendations, most of which I haven't read yet. :-)

Elantris is very underrated. Excellent book."Long Way..." is a good antidote to, well, everything currently happening in that's it's a hopeful future. Character driven (things definitely happen but there's no over arching plot).

I'll stick to a few older ones:
The Man in the High Castle
The Stars My Destination
Tigana
The Anubis Gates
The Moon is a Harsh Mistress
Starship Troopers
The Demolished Man
Emphyrio
Mythago Wood
The Princess Bride

One of my all-time favorites: Wild Seed

Other threads where this came up in the past for easy reference:

Standalone High Fantasy: /topic/show/...

Stand-Alone Fantasy Novels: /topic/show/...

List of Best Stand-Alone Fantasy Books: /topic/show/...

Good Stand Alone Books: /topic/show/...

Stand Alone Books? /topic/show/...

Of course, many of these are older threads, so links may no longer be active, but may be helpful? Or not.

Although Chasm City is set in the Revelation Space universe it's a stand alone.