Sodium borohydride, NaBH4, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells(PEMFCs). Properties of NaBH4 hydrolysis reaction using unsupported Co-B, Co-P-B catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of NaBH4 concentration and durability of catalyst were measured. The BET surface area of unsupported Co-B catalyst was 75.7 m2/g and this value was 18 times higher than that of FeCrAlloy supported Co-B catalyst. The hydrogen yield of NaBH4 hydrolysis reaction by unsupported catalysts using 20~25 wt% NaBH4 solution was 97.6~98.5% in batch reactor. The hydrogen yield decrease to 95.3~97.0% as the concentration of NaBH4 solution increase to 30 wt%. The loss of unsupported catalyst was less than that of FeCrAlloy supported catalyst during NaBH4 hydrolysis reaction and the loss increased with increasing of NaBH4 concentration. In continuous reactor, hydrogen yield of NaBH4 hydrolysis was 90% using 1.2 g of unsupported Co-P-B catalyst with 3ℓ/min hydrogen generation rate.