Photocatalytic nitrogen fixation has become a hot topic in recent years due to its mild and sustainable advantages. While modifying the photocatalyst to enhance its electron separation, light absorption and nitrogen reduction abilities, the role of the active sites in the catalytic reaction cannot be ignored because the N^N nitrogen bond is too strong to activate. This review summarizes the recent research on nitrogen fixation, focusing on the active sites for N2 on the catalyst surface, classifying common active sites, explaining the main role and additional role of the active sites in catalytic reactions, and discussing the methods to increase the number of active sites and their activation ability. Finally, the outlook for future research is presented. It is hoped this review could help researchers understand more about the activation of the nitrogen molecules and lead more efforts into research on nitrogen fixation photocatalysts.