Abstract: Ammonia borane (AB) is recognized as a stable and safe hydrogen storage material, which renders it particularly advantageous for the advancement of a hydrogen economy. This study successfully demonstrates hydrogen production through the catalytic hydrolysis of AB utilizing cuprous oxide deposited on titanate nanotube arrays (Cu2O/TNAs) within a photoelectrochemical (PEC) system. The synthesis of Cu2O/TNAs was accomplished through the square wave voltammetry electrodeposition (SWVE) technique, followed by comprehensive characterization of their physical and chemical properties. The enhancement of PEC performance can be attributed to the high separation efficiency of electron-hole pairs, a result of the deposition of Cu2O nanoparticles. This phenomenon facilitated hydrogen production during the catalytic hydrolysis of AB. Experimental results indicated that the integration of Cu2O/TNAs with the PEC system constituted the most effective approach for hydrogen generation via catalytic hydrolysis of AB. This efficacy is derived from both the deposition of Cu2O nanoparticles and the synergistic interaction between photocatalysis (PC) and electrocatalysis (EC). Furthermore, a detailed mechanism and pathway for hydrogen production via catalytic hydrolysis of AB using Cu2O/TNAs within the PEC system are proposed to elucidate the involved redox reactions. In conclusion, this research provides substantial contributions to the application of high-performance photocatalysts and technologies for hydrogen production, reinforcing the significance of advancing energy solutions.