Transition-metal is known to catalyze peroxymonosulfate (PMS) decomposition to produce sulfate radicals. Here we report reactions between PMS and chloride, without a need of transition metals, also can be used to degrade organic dye pollutant (Rhodamine B, (RhB)). Some important operating parameters, such as dosages of PMS and Cl(-), pH of solution, temperature, ionic strength, and several common cations, were systematically investigated. Almost complete decoloration of RhB was achieved within 5 min ([PMS] = 0.5 mM, [Cl(-)] = 120 mM, and pH 3.0), and RhB bleaching rate increased with the increased dosages of both PMS and chloride ion, following the pseudo-first-order kinetic model. However, the total organic carbon (TOC) removal results demonstrated that the decoloration of RhB was due to the destruction of chromophore rather than complete degradation. RhB decoloration could be significantly accelerated due to the high ionic strength. Increasing of the reaction temperature from 273 K to 333 K was beneficial to the RhB degradation, and the activation energy was determined to be 32.996 kJ/mol. Bleaching rate of RhB with the examined cations increased with the order of NH4 (+) < Na(+) < K(+) < Al(3+) < Ca(2+) < Mg(2+). Some major degradation products of RhB were identified by GC-MS. The present study may have active technical implications for the treatment of dyestuff wastewater in practice.