It's still a great feat on any build that stacks critical damage high and puts points into stealth, namely snipers, plasma pistols and possibly crossbows. Situational, but when it works, it works wonders. You can easily reach 100% critical chance by the end of the game.
This video shows this pretty well:
https://www.youtube.com/watch?v=5hEIzls7qPcThat said sometimes it's hard to determine if the tile you are standing is completly dark and if the enemies are sufficiently illuminated. Generally enemies are sufficiently illuminated if:
1. They are standing right next to a fire barrel or other strong source of light such as wall lamps, etc.
2. They are standing right on top of a flare. Not next to it, the flare has to exactly under them
3. Close to the center of molotov flames
4. Inside very bright rooms
As for the illumination of the tile you are standing in, take a look at your portrait- if you see some flickering lights that means it's not totally dark.
I really feel there should be some sort of a indicator that shows whether the conditions for ambush are met or not. But beyond that, it really does work great.