Co-P-B catalyst coatings have been synthesized on Ni-foam by using electroless deposition (ED) and their catalytic activity was investigated by catalytic dehydrogenation of ammonia borane (AB, NH 3BH 3) for H 2 generation. Co-P-B catalyst (both in form of powder and coating) showed superior catalytic activity in hydrolysis reaction of AB than that of Co-B powder, with complete evolution of H 2 (97%) at very high rate (2l/min/gcatalyst). This was mainly attributed to synergic effect caused by B and P over Co active sites to lower the activation energy of the process. For thermolysis reaction, it was observed that AB loaded on Co-P-B/Ni catalyst releases first mole of H 2 at considerably low temperature starting at 50°C and with desorption peak centered at 80°C. To our knowledge this value is the lowest reported for solid state catalyst. Moreover, the catalytic thermolysis did not present any induction time and minimizes the formation of undesirable byproduct like borazine and ammonia. The present result suggests that Co-P-B coated on Ni is a highly efficient and low cost catalyst and can be used for both hydrolysis as well as thermolysis reaction of NH 3BH 3 with the important advantage that it can be easily recovered and repeatedly reused.