I used to do that kind of thing at work. But usually not directly intentionally. Whenever a disk on a server grew significantly faster than normal, I'd fire up a utility that visualized file space utilitization. There's always clusters of obvious stuff. Most often videos or pictures not of a professional nature. Unless it was something I couldn't ignore, I'd call the owner of said files and say "look, I don't care what you put on my server and I ain't prying. But I need the disk space, so if it's not work related move it elsewhere. Now." Folks never just say ok and do it, they always try to come up with some excuse. If it was uh, worrisome, I'd notify HR.
Only had one 'legit' case where someone dumped multigig files on the server. He had been keeping critical CAD drawings on his PC and wanted to back them up on his personal share. So he berated me for questioning his utilization, when I asked why he dumped 60 gigs on my server with no notice. Until his department VP asked the logical question, why was he storing it locally instead of with the other CAD projects like he was told? Never heard from the guy again.
I don't snoop on personal files for chuckles. I don't have the spare time. I don't get the desire to do so either. There's nothing interesting on someone's laptop that you can't find on the internet. Guess some folks just get off on the whole invasion of privacy thing. Same reason we have peeping Toms.
Oh, there IS one legit way of accidently snooping in the normal course of business. If you're copying files, you see the folder names. Big folders stick on the screen longer. When you do it for a living, you also know how long it's normally supposed to take to copy files. If a folder named "Accounts Receivable Q3 2005" or whatnot takes five minutes to copy over gigabit ethernet (when it'd normally take seconds), you know it's a video stash.