It's called a 'Flamin Lamborghini', which is a combination of Sambuca and Kahlua in a shot glass and set on fire. In the video you can see the customer attempt to take the shot after being lit by the bartender and catch his whole face on fire. This is a shot that is very dangerous to take and wouldn't recommend it, especially after seeing all these videos of people catching their face on fire.

Credit [Youtube]