Nano-zero valent iron/kaolinite (nZVI/kaolinite) composite was prepared by liquid-phase reduction method in the presence of sodium borohydride. Transmission Electron Microscope images demonstrated that spherical nZVI particles with oxide layer were successfully engaged into the kaolinite surface and edges, which was beneficial to the peroxymonosulfate (PMS) activation and bisphenol A (BPA) degradation. The prepared nZVI/kaolinite composite was endowed with excellent performance in removing BPA with the assistance of PMS, namely more than 95% BPA could be eliminated in 15 min. In contrast with alkaline environment, weak acid and neutral environment were more advantageous to the BPA degradation. All the anions like Cl−, SO42−, HCO3− and H2PO4− were adverse to the BPA degradation in nZVI/kaolinite/PMS system. Furthermore, EPR and radical quenching experiments proved that SO4•− and 1O2 were the main active components during the series reactions. The possible degradation pathways were also inferred based on the liquid chromatography-mass spectrometry (LC-MS) results. Besides, the nZVI/kaolinite composite displayed good performance toward coking wastewater as well. This study is of great significance in designing of efficient persulfate activated materials and treating wastewater.