Yes it would work. As was pointed out a few replies up, you need to match the novec product with the temps you want to aim for.

It is evaporating. If you did it in an open container, it would all eventually boil away: just like if you boiled a pot of water on a stove for long enough. The idea here is that you operate it in a closed or semi-closed environment, where the evaporated gas vapor is then condensed on some cool object (a heat exchanger or heat sink of some type). The condensed liquid will then drip down back into the bulk of the liquid around the hardware being cooled and this process repeats indefinitely. It's actually the same thing that is happening inside every fridge/freezer and air conditioner, except this time we're cooling something that's inside the cooling loop itself.

I suspect that smracer has a good deal of capital to throw at this project. And I suspect he's partly doing it for fun too. The reason I say this is that these liquids are extremely expensive ($250-350 per litre usually) and results in a relatively complicated system compared to using normal heatsinks and fans. Usually the only reason to do phase change submersion cooling on a large/commercial scale is to obtain obscenely high hardware densities, where space is of #1 importance. For example, this case:  http://hongwrong.com/hong-kong-bitcoin/