For practical application of sodium borohydride (NaBH[Formula: see text] hydrolysis to generate hydrogen, metallic catalysts with low cost but excellent activity are highly desired. However, it remains a big challenge to further improve the activity of non-noble metal catalysts. In this work, photocatalysis technology was successfully introduced to enhance the catalyst activity for NaBH4 hydrolysis. By means of conventional impregnation-reduction method, CoB nanocatalyst was evenly deposited on graphitic carbon nitride surface, resulting in a Schottky-type photocatalyst (CoB/CN). As expected, hydrogen generation rate was greatly boosted owing to light irradiation. According to the results of capture experiments, photoexcited electron from g-C3N4 could enrich the electron density of CoB surface, which leads to the improvement of catalyst activity. Additionally, the light irradiation facilitates the remarkable decrease of apparent activation energy. Compared with some reported noble metal catalysts, the CoB/CN presents higher activity, especially under light irradiation.