This paper reports on the use of Co supported catalyst for the hydrolysis of NaBH4. Various materials with different acid/base surface properties have been chosen as supports (hydrotalcites, KF/Al2O3, heteropolyanions). The supports and the Co-containing catalysts were characterized by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, nitrogen adsorption. The NaBH4 hydrolysis reaction was studied in a liquid phase calorimeter coupled with a gas counter in order to follow at the same time the kinetics and the heat of reaction. Co supported on heteropolyanions showed great results in terms of reaction rate. Cobalt dispersed on heteropolyanions is a real promising catalytic system for the development of hydrogen generation in PEM fuel cells for portable devices. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.