Developing a high efficiency, stability and low cost catalytic electrode is of great practical significance to reduce the overpotential of hydrogen evolution. For this reason, NiB@Fe–B/PU catalytic electrode on non-conductive base material polyurethane sponge (PU) was prepared by a mild electroless plating method in this work. NiB@Fe–Co–B/PU, NiB@Fe–Mo–B/PU catalytic electrode were successfully prepared by doping a small amount of the third element, such as cobalt, molybdenum and other metal elements to improve its hydrogen evolution performance in neutral electrolyte solution. The results showed that the performance of NiB@Fe–B/PU catalytic electrode had significant improvement by doping of cobalt and molybdenum, and the performance of doping cobalt was better. The overpotential was only 161 mV(current density, j=50 mA/cm2) and the Tafel slope was 68.24 mV/dec for NiB@Fe–Co–B/PU catalytic electrode to hydrogen evolution reaction (HER) in 0.5 mol/L phosphate buffered saline (PBS). At the same time, the electrode showed good stability, which can work stably for more than 24 h under the overpotential of 61 mV.