Novel FeS/kaolinite composite (K-FeS) were successfully prepared using an in-situ precipitation method. At 30 % FeS loading, 1 g/L of the composite material by activating peroxymonosulfate (PMS) was able to completely remove 20 mg/L benzo[a]pyrene (BaP) and 40 mg/L Cr(VI) within 20 min under optimized conditions. The simultaneous removal experiments of BaP and Cr(VI) for the influence factors of BaP concentration, Cr(VI) concentration, composites dosage and PMS dosage to be 20 mg/L, 40 mg/L, 1 g/L, and 0.75 mmol/L, respectively. Experiments on environmental factors show that low temperature and acidic conditions are more favorable for material activity, and the addition of Cl- could promote the removal of BaP and Cr(VI). Comparative experiments showed that the simultaneous presence of BaP and Cr(VI) did not affect the removal of each other. The pseudo second-order kinetic model and Langmuir adsorption isotherm model were better to fit the experimental data, and the thermodynamic analyses indicated that the removal processes of BaP and Cr(VI) were spontaneous and exothermic. Besides, the quenching experiments yielded that SO4− and OH played a dominant role in BaP removal, and Cr(VI) removal mainly depended on the reduction of composites. This study expands the application of clay minerals in water treatment and suggests new strategies for simultaneous treatment of multiple pollutants in the environment.