Ammonia borane (NH₃BH₃, AB) holds promise for chemical storage of hydrogen. However, designing superb and low-cost photocatalyst to drive hydrogen evolution from AB under visible light irradiation is highly desirable but remains a major challenge for promoting the practical utilization of AB. Herein, we demonstrated a heterostructure photocatalyst consisting of zero-dimensional (0D) CoP nanoparticles immobilized on two-dimensional (2D) Co₂P nanosheets (CoP/Co₂Ps) as a high-performance and low-cost catalyst for hydrogen evolution from AB hydrolysis, in which 0D/2D heterostructure was synthesized using the salt-induced phase transformation strategy. Interestingly, the optimized CoP/Co₂Ps exhibit a robust H₂ evolution rate of 32.1 L∙min⁻¹∙g_Co⁻¹, corresponding to a turnover frequency (TOF) value of 64.1 min⁻¹, being among the highest TOF for non-noble-metal catalysts ever reported, even outperforming some precious metal catalysts. This work not only opens a new avenue to accelerate hydrogen evolution from AB by regulating the electronic structures of heterointerfaces, but also provides a novel strategy for the construction of precious-metal-free materials for hydrogen-related energy catalysis in the future.