The traditional synthesis of ammonia is an industrial process with high energy consumption that is not environmentally friendly; thus, it is urgent to develop cost-effective approaches to synthesize ammonia under ambient conditions. In recent years, the photochemical synthesis of ammonia has become a hot research frontier. In this mini review, we summarize the recent advances in materials sciences for photocatalytic nitrogen fixation. Beyond nitrogen fixation, we talk about an alternative for artificial ammonia synthesis and coupling reactions with other reactions for the synthesis of other high-value chemicals. The results and findings of this review will help the development of ammonia synthesis and the synthesis of other high-value chemicals.