Lol sure if you use a fuckload of gasoline in a poorly ventilated setting. You've gotta be pretty dumb to bask in fumes like that.
Pour out like half an ounce onto a paper towel, outdoors? Don't let it sit. Put the can far away. Use a long grill lighter... You'll be fine.
The trick to using it as a firestarter is, indeed, that it's the fumes that burn - it needs a wick to work best, and that assembly goes 6-12" under the firewood...