Yes, I know this is an old one that sooo many people have asked before... but its been a long time since I had a working LMCE system running, and even then it was a bit dodgy!
I set up a Hybrid in a VM, added a network drive from another PC (actually the VM host - XP), let LMCE find it, told it to use it, public and in the LMCE standard structure. Confirmed that it had successfully created the public-data-audio/video, etc folder structure - so it can see/read/write the share OK. Then put some audio and video in the right folders - confirmed in the Admin page that it could see the share "device" under the right folders (Windows [30], etc) and clicked Resync on each. Watched the sync process happen thru completion.
Checked in the web admin media browser - can see media, but for some reason it only seems to show audio files no matter how many of the properties boxes I tick on!
Either way - in the LMCE media browser I cannot see anything in the appropriate media folders (except things like the Flickr folder). At this point I assumed it was the old mistake of not having tagging on files set up, so of course I just switched the sort mode to Filename - but still nothing!
Weird thing is, when I use the search dialogue, I can see all the media listed - audio and video?!