The main use for phosphorus tribromide is for conversion of primary or secondary alcohols to alkyl bromides, as described above. PBr usually gives higher yields than hydrobromic acid, and it avoids problems of carbocation rearrangement- for example even neopentyl bromide can be made from the alcohol in 60% yield.
Another use for PBr is as a catalyst for the α-bromination of carboxylic acids.  Although acyl bromides are rarely made in comparison with acyl chlorides, they are used as intermediates in Hell-Volhard-Zelinsky halogenation.
Initially PBr reacts with the carboxylic acid to form the acyl bromide, which is more reactive towards bromination.  The overall process can be represented as
On a commercial scale, phosphorus tribromide is used in the manufacture of pharmaceuticals such as alprazolam, methohexital and fenoprofen. It is also a potent fire suppression agent marketed under the name PhostrEx.
Phosphorus tribromide is used for doping in microelectronics.