Electrodeposited nickel-molybdenum, nickel-tungsten, cobalt-molybdenum, and cobalt-tungsten were characterized for the hydrogen evolution reaction (HER) in the electrolysis of 30 w/o KOH alkaline water at 25-degrees. The rate-determining step (rds) of the HER was suggested based on the Tafel slope of polarization and the capacitance of electrode-solution interface determined by ac impedance measurement. The HER on the nickel- and cobalt-based codeposits was enhanced significantly compared with that on the electrolytic nickel and cobalt with comparable deposit loadings. The decrease in the HER overpotential was more pronounced on the molybdenum-containing codeposits, particularly on cobalt-molybdenum which also showed a high stability. The enhancement of the HER was attributed to both the synergetic composition and the increased active surf ace of the codeposits. The real electrocatalytic activity of the electrodes and the effect of their surface increase were distinguished quantitatively The linear relations between HER overpotential and surface roughness factor of the electrodes on a Y-log(X) plot were obtained experimentally and interpreted based on the Tafel law.