VLC for Windows 8.1 is now available on the store! It is the same link for Windows 8, and you can find the download link below (again, only for 8.1 users). Do note that if you have the current VLC for Windows 8 (the metro version, not the desktop) and you can't upgrade to the latest version, try uninstalling the older version beforehand.
The Windows 8.1 application is a completely new design; you have a way to navigate by a very simple menu on the left, instead of the top. There is a search bar, followed by a home, videos, and music tab. The home view gives you a snapshot of your video and audio library.
Personally, I can't get it to actually work. That may be because I am running the Windows 10 Technical Preview (but they showed it off on Windows 10 last night). Every time I open it up, it goes away in a second. In fact, the only way I got a screenshot was that it froze while crashing. We'll update as we test it (the link is not updated for everyone either).
The VLC project for Metro UI has been plagued by delays, so we're just happy its out.
Warning: There are a few FAKE apps out there that claim to be VLC. ESPECIALLY if they are charging. The download link (below) will take you to the official version.
Update: If you are experiencing the same problem as me, look at the steps here, they solved the crashing problem for me. Thanks saschanaz!