Developing a highly efficient and stable photocatalyst or co-catalyst is one of the important topics in the field of photocatalysis research. In this study, graphene oxide, cobalt chloride and 2-methylimidazole were used as precursors to prepare Co_5.47N-loaded nitrogen-doped reduced graphene oxide (Co_5.47N/N-rGO) co- catalyst by combining liquid phase method and nitridation in flowing NH₃ where Co_5.47N with a crystallite size of 10~20 nm was highly dispersed over N-rGO surface. The Co_5.47N/N-rGO co-catalyst significantly improves the hydrogen evolution performance of commercial nano TiO₂ (P25). When the mass percent of Co_5.47N/N-rGO was 25%, the hydrogen evolution rate of the obtained sample reached 11.71 mmol·h ^-1·g ^-1, which was 90 times higher than that of pure P25 and similar to that loaded noble metal Pt (11.88 mmol·h ^-1·g ^-1). Furthermore, the catalyst also has good stability. The research provides a new idea for the future development of efficient non-precious metal co-catalysts.