Ternary catalyst Cobalt-Manganese-Boride (Co-Mn-B) has been synthesized with chemical co-precipitation followed by calcination at various temperatures. The effects of heat-treatment temperature on the catalytic activity toward hydrolysis of alkaline NaBH4 solution have been comparatively investigated and analyzed using various techniques including X-ray diffraction (XRD), Differential Scanning Calorimetry (DSC), Scanning Electron Microscope (SEM) and BET surface area. The effects of NaOH and NaBH4 concentration as well as reaction temperature on hydrogen generation rate from alkaline NaBH4 solution catalyzed by the optimal Co-Mn-B catalyst have been studied. The results, along with the calculated activation energy, have been analyzed and discussed. It is revealed that the Co-Mn-B catalyst heat-treated at 250 degrees C has the highest catalytic activity with an activation energy of 52.1 kJ mol(-1) mora, the hydrogen generation rate catalyzed by it is 45% higher than that by Co-B catalyst. Crown Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.