The decomposition of sodium dodecylbenzene sulfonate (SDBS), which is a dangerous and anionic surfactant, was investigated by the electro/Fe2+/persulfate process from aqueous solutions. The activation of persulfate anion and production of active radicals were performed by means of heat, UV and iron ions (released from iron electrodes). The finding illustrated that the pH value of the solution, initial concentration of persulfate anion, the amount of input voltage and iron dosage were entirely effective in SDBS removal. Nearly 100% of SDBS was removed under the optimum conditions: pH 3, voltage 10 V, anion persulfate concentration 25 mM/L, iron ion dosage 0.25 g/L and reaction time 25 min. Furthermore, the application of the persulfate anion process in concert with the electrochemical process, in order to generate electrical iron and persulfate activation, had a better performance compared to separate methods.