The development of high-performance and low-cost electrodes is essential for hydrogen production using a proton exchange membrane water electrolyzer (PEMWE). Herein, we report an electrochemical method for the fabrication of a Ni-P based cathode for a PEMWE single cell. A porous copper foam (CF) is fabricated on carbon paper (CP) by two-step electrodeposition to obtain a large number of active sites for Ni-P formation. The high conductivity of the Cu metallic support is expected to reduce the charge transfer resistance. After the Ni-P electrodeposition on CF, an anodic leaching process is conducted for the selective dissolution of the excess Ni metal formed during the electrodeposition, thus enabling the modification of the electronic structure of the catalyst. The electrode optimized in halfcell tests is used as the cathode for a PEMWE single cell. The PEMWE cells exhibit a current density of 0.67 A/cm2 at 2.0 Vcell which is higher than or comparable to the performance previously reported in the literature.