Textile effluents containing synthetic refractory azo dyes are one of the most important sources of water pollution. However, these kinds of refractory organic pollutants did not resist a persulfate (PS) oxidation process which was correctly activated. In this study, PS was activated by ferrous sulfide (FeS) in a heterogeneous system to break down azo dyes wastewater. The results showed that all five selected azo dyes were efficiently broken down using the PS/FeS system, except for DY 12, and more than 95% of azo dyes were decolored within 60 minutes. The decolorization efficiency of DR 81 in the PS/FeS system was comparable to PS activated with heat (60 °C) or Fe2+, and was slightly superior to Fe0 powders under the same conditions. Quenching studies indicated that both SO4-• and •OH were formed in the FeS surface and diffused into the solution to facilitate the successive transformation of DR 81, the •OH reaction with DR 81 might the crucial reaction. The coexisting chelating agents in real azo dye effluents at high concentrations had a negative influence on azo dye decolorization by PS/FeS. However, the superior factor of the PS/FeS system was the regenerability and reusability of the heterogeneous catalyst.