Will it work? Absolutely as long as you can map the networked storage into something native to the OS that the application understands. Basically for Windows, this means you just need to map it to a drive letter using the Map Network Drive function. Linux and the like is probably similar: just make it so the network path can be resolved like a local path.
Also it is possible to play games even over WiFi (I've done this before). My test game was GTAV, and it worked perfectly fine on 802.11ac. It was still technically playable on 802.11n, but the world wasn't exactly there. So you could probably still play over 802.11n assuming the game doesn't stream assets in. Obviously though, you should play over a hardline for maximum performance/reliability.