With the rapid electrochemical development of hydrogen evolution, the search for low‐cost and high activity electrocatalysts for hydrogen evolution has received extensive attention. The fabrication of self‐supported Cu 2 S‐Cu 3 P nanowire (Cu 2 S‐Cu 3 P NW) arrays on a commercial copper foam by a liquid–solid reaction and subsequent phosphatation at low temperature is reported. The corresponding scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results indicate that the Cu 2 S‐Cu 3 P NW arrays have a dense nanowire (NW) structure with sulfur and phosphorous uniformly distributed on the surface of the nanowires. Interestingly, the Cu 2 S‐Cu 3 P NW arrays act as a hydrogen‐evolving cathode that when operated in 1.0 m KOH electrolyte only require a low overpotential of 158 mV to achieve a current density of 10 mA cm −2 and show a small Tafel slope of 45 mV dec −1 . The activity decrease is negligible after holding at −500 mA cm –2 for 75 h, which thus demonstrates excellent stability. This could be due to the structure of nanowire arrays and synergistic effects between S and P, which could increase the specific surface area, reduce the charge transfer resistance, facilitate mass diffusion and electron transfers, and increase the active sites. This work therefore provides a simple method to prepare low‐cost and self‐supported electrocatalysts with high catalytic activity for hydrogen evolution.