Ammonia production through the photoelectrochemical nitrate reduction reaction (PEC NO3RR) is undergoing significant advancements to improve efficiency and selectivity. Researchers are exploring innovative photocathodes and cocatalysts to address challenges such as low solar-to-ammonia efficiency and poor selectivity inherent in the process. By developing bias-free systems that couple ammonia production with value-added product generation like glycerol oxidation, the field is moving towards sustainable applications. Recent studies have highlighted the successful integration of novel photocathodes like CuOs/CdS/SSS and photoanodes such as ruthenium-doped bismuth oxide to achieve high solar-to-ammonia productivity with selective production of valuable chemicals. These advancements have resulted in impressive performance metrics, including high Faradaic efficiencies for both ammonia production and glycerol oxidation, stable operation, and low onset potentials, showcasing the potential for further progress in the field.