Fe-Co-W alloys have been developed by using suitable bath solution and plating conditions. The alloys are characterised for use as stable and low hydrogen overvoltage cathode material for the hydrogen evolution reaction in alkaline solution. The developed alloys (Fe:Co:W 20:68:12) exhibited an overpotential of 0.120V for about 80 hrs of continuous electrolysis in 30% KOH at a cd of 100 mA/cm 2 and temperature 343K. Electrocatalytic activity was found to vary with composition and structure of the alloy deposits. X-ray diffraction and cyclic voltammetric studies revealed the existence of several phases in the alloy. Impedance studies at different temperatures and overpotentials indicated the temperature dependence of the HER reaction mechanism, desorption of the intermediate species and electron transfer on the surface, each one competing depending on the experimental conditions. This has been further confirmed by the electrochemical parameters observed.