NBr3 was first prepared by reaction of bistrimethylsilylbromamine (bis(trimethylsilyl)amine bromide) with bromine monochloride (with trimethylsilyl chloride as byproduct) at −87 °C according to the following equation: where "Me" is a methyl group.

NBr3 can be produced by the reaction of bromine or hypobromite and ammonia in a dilute aqueous buffer solution.

[4] Ammonia and bromine undergo glow discharge, and after treatment, red NBr3·6NH3 can be obtained.

[6] Nitrogen tribromide reacts instantly with ammonia in dichloromethane solution at −87 °C to yield NBrH2.

[7] It also reacts with iodine in dichloromethane solution at −87 °C to produce NBr2I, which is a red-brown solid that stable up to -20 °C.