A novel method of synthesis of organic ammonium tribromides (OATBs) is developed by using an inexpensive and eco-friendly sodium hypochlorite as oxidant for conversion of Br- to Br-3(-). The OATBs thus prepared include both quaternary ammonium tribromides and N-heterocyclic tribromides. A new addition to the family of OATBs is made in the form of phenanthroline hydrotribromide. The efficacy of this new tribromide as catalyst is ascertained in the oxidative transformation of organic sulfides to their corresponding sulfoxides and sulfones by hydrogen peroxide.