The p-n junctions composed of ZnO nanosheets and MoS2 nanoparticles were facilely immobilized on Ni foam by two-step electrodeposition method for efficient degradation of organic pollutants through the photoelectrocatalytic (PEC) process. This unique strategy incorporates two semiconductors into p-n heterojunctions on three-dimensional Ni foam substrate, which can enhance visible-light absorption, inhibit the recombination of photogenic charges and expose abundant active sites for photocatalytic oxidation. Thus, the resulting fabricated hybrids (Ni foam@ZnO/MoS2) directly acting as working electrode performs a highly efficient degradation of organic pollutants in water through PEC process that can promote the separation of photogenerated electron-hole pairs under the low applied voltage. In addition, Ni foam@ZnO/MoS2 shows excellent cycling stability and can be easily separated for recycled PEC process, which is advantageous for further application in environmental purification.