Definitely available in Word 2016. Go to File|Options|Quick Access Toolbar>All Commands:Select All.
If you can't find it there, that suggests your Office installation has developed a fault. Try repairing it.
Personally, though, I think using that would have to be waaay slower than just pressing Ctrl-A.
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Cheers,
Paul Edstein
[Fmr MS MVP - Word]
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