See, oranges like to attract animals to eat the fruit so they’ll “pass along” the seeds so further generations of oranges can grow. Basically, the circle of life at work. However, not everything that eats oranges can and/or will pass along these seeds, namely mold and insects; they just like the sugar. So, in order to protect itself, the orange has a system of pouches in the peel that hold an oil. When a pouch is ruptured by, say, a hungry insect, the oil spurts forth and kills the intruder. It just so happens this oil is also flammable, so if you squeeze some on an open flame… well, I’m sure that’s self-explanatory.
tl/dr: Orange peel oil is flammable. Just watch the video above.
Just remember that Tactical Fanboy in no way, shape or form is condoning playing/experimenting with fire and/or potentially dangerous natural oils. It’s simply for entertainment purposes only.
Hat tip: io9