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Electrolytic water splitting is the most effective approach for the production of oxygen and hydrogen as it uses water as a feedstock which is non-toxic, green, and inexpensive. Hydrogen generation by electrolysis of water is an important process for the production of renewable energy resources. The high cost, less abundance, poor stability, and carbon monoxide poisoning of currently used noble metals as electrocatalyst is the bottleneck of this technology. These limitations can be conquered by using transition metal phosphates. In particular, cobalt phosphate-based materials show favorable performance and stability for electrolytic water splitting. Furthermore, cobalt phosphates in combination with semiconductors act as a co-catalyst in solar water oxidation. The variable oxidation state of cobalt is beneficial for fast electron transfer. The phosphate group due to its unique lattice structure helps in the adsorption and dissociation of water on the surface of the electrode. This review will provide a brief outline of the structure and activity relation between cobalt phosphate-based materials. The electrocatalytic applications of these materials in water oxidation, hydrogen generation, and overall water splitting have also been discussed. The role of cobalt phosphate-based materials in water splitting using solar radiation is thoroughly explained. In the end, a diverse range of synthesis methods, challenges, and future prospects have been presented. [ABSTRACT FROM AUTHOR]