The issues of hydrogen generation and storage have hindered the widespread use and commercialization of hydrogen fuel cell vehicles. It is thus highly attractive, but the design and development of highly active non-noble-metal catalysts for on-demand hydrogen release from alkaline NaBH4 solution under mild conditions remains a key challenge. Herein, we describe the use of CoP nanowire array integrated on a Ti mesh (CoP NA/Ti) as a three-dimensional (3D) monolithic catalyst for efficient hydrolytic dehydrogenation of NaBH4 in basic solutions. The CoP NA/Ti works as an on/off switch for on-demand hydrogen generation at a rate of 6,500 mL/(min·g) and a low activation energy of 41 kJ/mol. It is highly robust for repeated usage after recycling, without sacrificing catalytic performance. Remarkably, this catalyst also performs efficiently for the hydrolysis of NH3BH3.