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My bluetooth controller emulates an xbox 360 controller, but, even if it reports 16 buttons, it actually has 15 buttons. It doesn't have the home button.
There's a way to map a different key combination to open the overlay?
Also: looks like the maker of my controller cheaped out a little bit with electronics, so start+select can't be pressed at the same time (if you press one, the other will be depressed)
Go to 'Steam' > 'Settings', and from there to the 'In-Game' tab.
There's an 'Overlay shortcut keys' box, where you can change the key-binding to anything you like:
In 'Settings', there's also a tab dedicated to Controller settings:
Because I don't have a controller to test this out, I can't see whether or not there is an option there to change the controller keybinding for the Steam Overlay, but the possibilities seem quite extensive anyway.
Here's an in-depth guide on How-To-Geek.
