In this study, different double-supported Co-Cu-B/g-C3N4/Ni foam (NF=Ni foam) catalysts were synthesized by chemical deposition method in a certain pH value range (pH value between 10.5 and 12.0). Their catalytic performances of hydrolyzing ammonia borane (NH3BH3) hydrolysis were investigated to produce hydrogen at 298 K. Because of the adding of g-C3N4 in the plating solution, the obtained sample had certain photocatalytic activity when the visible light was introduced the hydrolysis experiment. The results displayed that the as-prepared Co-Cu-B/g-C3N4/NF catalyst at pH = 10.5 exhibited an improved catalytic effect for NH3BH3 hydrolysis under visible light irradiation. The corresponding hydrogen generation rate reached 8893 mol·min−1·g−1, and the activation energy was 41.8 kJ·mol−1. The catalytic performance of Co-Cu-B/g-C3N4/NF catalysts prepared by this method is better than that of as-obtained mono-metal Co-B/g-C3N4/NF catalyst. More importantly, its activity has exceeded many single-carrier cobalt-based catalysts reported so far, and even some single-support precious metal catalysts for NH3BH3 hydrolysis. It indicated that the strategy of double carriers and introduction of light contributed to the improvement in catalytic activity for the non-noble metal-based catalysts during NH3BH3 hydrolysis.