In this work, a novel cuprous sulfide (Cu2S) and cuprous oxide (Cu2O) decorated iron-based nanoparticles (INPs) were developed (Cu2S/Cu2[email protected], B denote bentonite) and applied for 2,4-dichlorophenol (2,4-DCP) degradation. The physicochemical properties of the as-prepared catalyst were characterized via SEM, TEM, BET, DRS, and EIS. Results of TEM images exhibited the deposition of copper species could improve the morphology and reduce the mean particles size effectively. Cu2S/Cu2[email protected] exhibited excellent catalytic performance to degrade 2,4-DCP by adsorption, Fenton-like oxidation and photocatalytic processes. Under optimal conditions, the degradation percentages caused by adsorption, adsorption-Fenton like and adsorption-Fenton like-photocatalytic processes were about 27.6%, 74.58% and 99.8%, respectively. Furthermore, GC-MS served to identify the intermediates and final products, a possible mechanism and degradation pathway for 2,4-DCP were proposed based on the intermediate by-products detection and active radicals’ detection. The reusability of Cu2S/Cu2[email protected] was achieved with four successive runs. Research provides a promising approach for the treatment of chlorophenols polluted water.