Designing effective photo electrode for photo-electrochemical (PEC) water splitting is highly demanded yet challengeable because of the limited sunlight utilization and retarded redox reaction kinetics. This work introduces a feasible one-pot hydrothermal strategy of fabricating MoS2/NiFe LDH p-n heterojunctions on conductive porous nickel foam as an efficient photoanode for PEC water splitting. A great enhancement for PEC water oxidation is achieved because of the improved sunlight absorption and the increased photo-excited charge separation. The optimal 10% MoS2/Ni0.9Fe0.1 LDH/nickel foam photoanode demonstrates 3.8 times enhanced PEC activity than the Ni0.9Fe0.1 LDH/NF counterpart and a low Tafel plot of 54 mV dec−1. The bandgap modulation and the Z-scheme charge transfer dynamics due to the formation of MoS2/NiFe LDH p-n heterostructure, along with the high conductivity of porous nickel foam account for the increased photo-current conversion efficiency and the boosted charge transfer.