The dehydrogenation of ammonia borane (AB) is an effective method to produce and store hydrogen, but efficient, durable, and low-costing dehydrogenation catalysts are lacking. In this work, we successfully prepared a self-supported bunch-like copper oxide nanowire array on copper foam (b-CuO NA/CF) through a facile in situ wet oxidation and annealing method. b-CuO NA/CF shows high catalytic activity for the methanolysis of AB with an initial turnover frequency of 13.3 mol H2 mol CuO −1 min −1 and an activation energy of 34.7 kJ mol −1 . Moreover, this self-supported bunch-like nanoarray catalyst could be easily separated from fuel solutions with excellent stability and maintained its activity even after prolonged use. It is thus an efficient, economical, and durable catalyst for hydrogen fuel cells.