Photocatalysis delivers a promising pathway toward the clean and sustainable energy supply of the future. However, the inefficiency of photon absorption, rapid recombination of photogenerated electron-hole pairs, and especially the limited active sites for catalytic reactions result in unsatisfactory performances of the photocatalytic materials. Single-atom photocatalysts (SAPCs), in which metal atoms are individually isolated and stably anchored on support materials, allow for maximum atom utilization and possess distinct photocatalytic properties due to the unique geometric and electronic features of the unsaturated catalytic sites. Very recently, constructing SAPCs has emerged as a new avenue for promoting the efficiency of sustainable production of fuels and chemicals via photocatalysis. In this review, we summarize the recent development of SAPCs as a new frontier for cocatalyst/photocatalyst composites in photocatalytic water splitting. This begins with an introduction on the typical structures of SAPCs, followed by a detailed discussion on the synthetic strategies that are applicable to SAPCs. Thereafter, the promising applications of SAPCs to boost photocatalytic water splitting are outlined. Finally, the challenges and prospects for the future development of SAPCs are summarized.