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I know that I can boot into Windows and start a specific program instead of explorer.exe. What I'd like to do is optionally boot into Windows with a different shell based on a selection I make in grub. Is this possible?

I'm dual-booting Windows and Linux, and I'd like to have an additional menu item in Grub that lets me boot into Windows and automatically start Steam in Big Picture mode without preventing me to boot into windows with the standard explorer.exe shell. SteamOS is not an option since several of my games are Windows only.

Is this at all possible?

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I don't know if this qualifies as answer or not but userinit.exe checks Current User's Shell before turning to Shell value in HKLM. Thus, each user can have their own Shell. So, you can create a new user and go to this registry key (make sure you are logged in as that user):

HKEY_CURRENT_USER\SOFTWARE\Microsoft\Windows NT\CurrentVersion\Winlogon

(Note that the key is in HKCU not HKLM)

You most probably won't find a registry entry named Shell there, so just right click on Winlogon, go to New and click on String Value. Name this new entry Shell and enter value as cmd.exe (just an example, replace it with the application you want to start).

This will start the specified program instead of explorer.exe whenever you log in as that user. So, without having extra boot entry, you can have both Windows Explorer and Steam as your Shell in two different users.