In this study, Co-B based quaternary alloy catalysts were synthesized for use in NaBH4 hydrolysis. Lanthanum (La) and tungsten (W) metals were added to Co-B catalyst by chemical reduction method. The effect of metal content (La and W), NaBH4 concentration, NaOH concentration, catalyst amount and temperature parameters were investigated in NaBH4 hydrolysis. Activity results show that the hydrolysis reaction rate first increases and then decreases with increasing NaBH4 concentration as well as NaOH concentration. The activation energy of the hydrolysis for Co-La-W-B catalysts was calculated as 39.2 kJ / mol. The maximum value of hydrogen generation rate was 3280 ml / min. In terms of application, hydrogen produced in the presence of the Co-La-W-B catalyst was used in PEM fuel cell application. Average yield value according to power and ideal voltage and maximum power value of the system were determined as 57%, 73% and 1.4 Watt, respectively. This original study demonstrates that the Co-La-W-B catalyst can be used as an ideal catalyst for PEM fuel cell applications.