Catalytic hydrolysis of chemical hydrides with the use of NaBH4 is a safe and effective way to provide hydrogen fuel for new energy vehicles and portable electronic devices. Herein we developed a Cu and Mo promoted Co hierarchical composites (Co1-xCuxMoO4) for hydrolysis of NaBH4 via an easy synthesis route. FESEM analysis depicts that the morphology of Co1-xCuxMoO4 hierarchical composites varied significantly from irregular microsphere to marigold microsphere to rose like morphology with the increase in Cu (x) ratio with respect to Co (1 - x). Flower-like morphological architecture and crystal configuration empower the supported catalyst to exhibit a remarkable catalytic activity and outstanding catalytic activity was obtained for marigold-like Co0.9Cu0.1MoO4 catalyst with an H2 generation rate of 1005.7 mL min-1 g-1, which confirms existence of synergistic effect between Co, Cu and Mo. Lower loading of Cu in Co1-xCuxMoO4 supported the active sites of Co to increase its catalytic activity. Additionally, the catalyst exhibits good recyclability after five successive runs of hydrolytic reaction, making it a robust catalyst for hydrolysis of NaBH4 and could be considered as a potential catalyst for portable hydrogen fuel systems.