I'm wondering because getting a controller seems like it would be the simplest way to play stuff with a controller. The games I'd be looking at would be Blizzard games especially Diablo.
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You can play anything with any controller. Some work plug & play, some need extra software. But all of them work. :)
Maybe not anything, as RTS or some olderw games that doesn't have native controller support could ve tricky to get working properly.
But yeah, you can get PS3, PS4, 360, One, Wii and Wii U controllers working on PC without the need of getting extra adapters. Some will need unnofficial software, but you can play modern games without too much trouble.
I've been playing Star Wars Battlefront 2 Beta with it and it's running great. As others have said, just add as a non-steam game.
I've worked on getting the Steam controller working with Diablo 3, HotS, and Overwatch. 3rd party game launchers can make getting Steam to recognize what game you are playing (and therefore switch to your config for that game) problematic, and Battle.net and Origin are the worst offenders (GOG galaxy is not required to launch games and uPlay already works well with Steam).
The easiest way is to add the game's EXE file to Steam as a non-steam game. This works for both Diablo 3 and Overwatch but did not work for me with HotS but YMMV. Launching a Blizzard game directly requires you to type in your password and sometimes your username too, since it is not getting login credentials from Battle.net. Otherwise it works great, you can bring up the steam big picture overlay while playing and make changes to your game's config, just as you would with any Steam game, the only downside is that for non-steam games you don't have access to as many user made configs, so you might have to make the config yourself.
This guide might help.
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Diablo 3 is a lot of fun to play with the steam controller. You can set up the left stick to move your character using a mouse region, described here, and then some people use both touchpads as mouse input but personally I like to use the left touchpad as a touch menu for windows like Skills and Items, and the right touchpad as high sensitivity mouse and the gyro for low sensitivity mouse. I map spells to the triggers, bumpers, and grips so I have fast access to all of them. Then I use the face buttons for misc things like Teleport and Potion.