Bromination of 2-alkoxynaphthalene (2-ANP) and its derivatives with trimethyl benzyl ammonium tribromide (TMBATB) did not proceed smoothly even under reflux conditions. But the addition of microconcentrations of cetyltrimethyl ammonium bromide (CTAB) to the reaction afforded dramatic rate accelerations as well as good-to-excellent yield of the products ranging from 70% to 90%. Reactions underwent regioselective monobromination at 1-position of 2-alkoxynaphthalene. The rate of bromination has been followed conductometrically. The reaction kinetics indicated first-order kinetics in [2-ANP] as well as in [TMBATB]. Kinetic results in the presence of CTAB were explained on the basis of the Raghavan–Srinivasan model as applied to micelle-mediated bimolecular reactions.