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The Steam Deck is running a version of the Linux[en.wikipedia.org] operating system, highly modified into a custom distribution they're calling "SteamOS".
Since most PC games are made for Windows, Valve, in partnership with Codeweavers[www.codeweavers.com] have created Proton[en.wikipedia.org] which is a compatibility layer that allows Windows games to run under Linux. This is really the magic that makes the Steam Deck possible in the first place.
Proton is excellent, and most games for Windows run well under Linux now thanks to Proton. Still, compatibility isn't yet 100%. Valve has built-in system called Deck Verified that attempts to tell end-users at a glance if a game will be a good experience on the Deck or not. Even then, Proton development is rapid, and even games that didn't run yesterday may well run today.
There are still tons of games that the Deck Verified system haven't touched, but will actually run well anyway. You can check ProtonDB[www.protondb.com] to see a crowd-sourced rating for how well a game runs on Linux via Proton, including comments on how to fix compatibility for many games.
Keep in mind, there are some games that simply do not run. (Yet.) This is usually due to some aggressive anti-cheat that's been implemented. Examples include Destiny 2, Fortnite, and the newest Call of Duty.
Also infrequently, some games that used to work will sometimes get broken after an update. EA is notorious for this, as they're always forcing in their stupid launcher or shoe-horning in some awful proprietary anti-cheat, sometimes years after release.
In my experience, I would say, regardless of their "deck verified" rating, about 70% of games "just work". Another 20% work fine with some small adjustment, like using a different version of Proton. The final 10% don't work, either because of anti-cheat, or something else. Constant work on Proton means those games will probably work at some point in the future though.
I think they meant to say "Proton-GE".
It's a custom version of Proton created by Glorious Eggroll.[github.com] It can make some otherwise incompatible games work that refuse to work on mainline Proton.
The easiest way to install Proton-GE is to just install ProtonUP-QT[flathub.org]. Switch to the desktop mode of your Steamdeck, then launch the "Discovery Store", which is kind of like the built-in app store. Search for "ProtonUP-QT" and install it. Then launch it, and add the latest version of Proton-GE.
Switch back to gaming mode, and select "properties" for the game in question, then "compatibility" and select the version of Proton-GE you've just installed.
The previously mentioned ProtonDB[www.protondb.com] will sometimes suggest fixes including using particular versions of ProtonGE.
Not that you'll be constantly fighting your Steam Deck to get games to run. A very healthy majority of games just work with no tinkering at all, but it's nice to have options when you need them.
Quick note: The "Playable" category means the game run perfectly fine, but there are a few things that might make your experience less than optimal on the Steam Deck. Things like small text that would be hard to read on a 7" screen, or incorrect button prompts, perhaps showing keyboard keys instead of Xbox/Steam Deck buttons. A game will also get the "Playable" status if you are required to manually bring-up the on-screen keyboard to input some text like a name, or use the touchscreen to navigate a menu or something.
There is no guarantee that a non-working game would ever be playable on SteamOS. There are some that will likely never work on that OS. As already mentioned by several above, those MMOs that use Anti-Cheat which may not be supported on Linux.
Think about a game you would want to play. Then go to YouTube and search for "Steam Deck [game name]". This will start giving you an idea if the games you would want to play will work.
FWIW, more games work than don't. I'm not a MMO player so I only have one main title that doesn't work which is Madden '24. EA's new Anti-Cheat does not work on SteamOS. I still have a desktop PC so I stream it from my PC to my Deck to play it. This does mean though if you are a fan of EA games that have online components, they likely will not work on SteamOS going forward.