Two-dimensional catalysts, which are sensitive to visible light and have a photothermal effect, can be used to catalyse the release of H2 from sodium borohydride (NaBH4) are being actively explored in energy saving systems. In this work, oxygen vacancy enriched two-dimensional CoFe-layered double hydroxide (CoFe-LDH) derivatives (named as CoFe-x °C, x = 200–500) have been explored for NaBH4 hydrolysis catalyzed by photo-thermal synergy without external heat source. The CoFe-300 °C presents its initial hexagonal lamellar structure and has the highest concentration of oxygen vacancy. These unique properties guarantee its excellent photo-thermal synergistic catalytic performance, achieving hydrogen production rate of 1877.5 mmol g−1 h−1, and maintains high efficiency after 5 cycles. This enhanced photo-thermal synergistic catalytic mechanism is the •OH (generated from h+ and H2O) attacks BH4− (absorbed on Ov sites) to produce H2, the heat from photothermal conversion accelerates the adsorption ability and attacking rate. This study opens a new strategy for the synergistic photo-thermal catalytic hydrolysis of NaBH4.