About 10-20% of time, my machine boots to Metro instead of desktop. I have 64 bit Windows 8.1 and AVG anti-virus. Problem seems to have started with upgrade to 8.1. When it occurs, I typically just restart Windows and it works next time.
With Windows 8.1 Start8 simply sets the OS setting for booting to the desktop, so unless something is resetting that it should work 100% of the time.
Make sure you have Start8 1.31 installed.
It is 1.31.
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