I have the "Edward Kelly" achievement in Kingdom Come Deliverance due to brewing 15 types of potions. Only 3.3% of players have it, which is pretty high compared to most of the ones posted here, but it's still a little interesting. Brewing potions in the game is a bit boring, and you can easily buy all the ones you need, so it's understandable why few people would get it. I just kinda decided one day I wanted to get to auto-brew level of skill and that meant lots of potion. Might as well make as many different kinds as I can, and auto-brew requires you've done it once already anyway.
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Not extremely rare but this achievement almost me rage-quit.
Finished Hollow Knight 100% in Steel Soul. I don't typically chase achievements. I knew finishing Steel Soul was one, but didn't know if 100% would be another.

My sibling, why would you ever play witch it on an official server?
Mine is nothing special. It's Architect of Ruin from Shotgun King. You get it for doing some minor progress in the new-ish (not really anymore, but it used to be new) Charnier mode, nothing challenging at all, but I assume the reason only 0.6% of players have it is because everyone moved on from the game before that content dropped.
Some test achievement for a game I was developing, to check that the achievement integration and unlocking worked as expected. It later got replaced by the real achievements, but my Steam rarest achievement showcase still shows it, so I’m happy to keep it for the lols. Probably only me and a couple QA folks could possibly have it. Well and cheaters of course.
Well and cheaters of course.
yea it undermines Steam achievement collecting a bit that there has been an easily available achi unlocker out there for almost 2 decades
I have all the achievements for Final Fantasy 1
Not counting rare ones that are from brand new DLC, this is my rarest (Stellaris).

With another rare from a different space 4x game (Endless Space 2):

Edit to add the one I am the most happy with (Noita):


What game is that?? Ive done something similar in Gamble With Your Friends but there's no achievement for that in the game XD
3.1% of players for Dungeons of Dredmor
