Tertiary phosphines and their oxides react with oxalyl bromide to generate corresponding quaternary phosphonium salts, which can be further transformed as active intermediates to facilitate the bromination of alcohols and the dibromination of unsaturated hydrocarbons. This chemical process carries substantial research significance in the field of organic synthesis. In this study, two types of triaryl phosphine oxides and benzyl diaryl phosphine oxides containing alkyne groups were designed and synthesized. These compounds were then subjected to reaction with oxalyl bromide, resulting in the formation of novel benzophosphonium tribromides and trans-phosphoryl dibromoalkenes, respectively. These findings demonstrate variations from their reactions with oxalyl chloride. Furthermore, the benzophosphonium tribromide obtained can act as an alternative reagent for bromine, enabling the direct bromination of aromatics compounds, olefin, alkyne and acetophenone derivatives.