Photocatalytic water splitting is a sustainable technology for the production of clean fuel in terms of hydrogen (H₂). In the present study, hydrogen (H₂) production efficiency of three promising photocatalysts (titania (TiO₂-P25), graphitic carbon nitride (g-C₃N₄), and cadmium sulfide (CdS)) was evaluated in detail using various sacrificial agents. The effect of most commonly used sacrificial agents in the recent years, such as methanol, ethanol, isopropanol, ethylene glycol, glycerol, lactic acid, glucose, sodium sulfide, sodium sulfite, sodium sulfide/sodium sulfite mixture, and triethanolamine, were evaluated on TiO₂-P25, g-C₃N₄, and CdS. H₂ production experiments were carried out under simulated solar light irradiation in an immersion type photo-reactor. All the experiments were performed without any noble metal co-catalyst. Moreover, photolysis experiments were executed to study the H₂ generation in the absence of a catalyst. The results were discussed specifically in terms of chemical reactions, pH of the reaction medium, hydroxyl groups, alpha hydrogen, and carbon chain length of sacrificial agents. The results revealed that glucose and glycerol are the most suitable sacrificial agents for an oxide photocatalyst. Triethanolamine is the ideal sacrificial agent for carbon and sulfide photocatalyst. A remarkable amount of H₂ was produced from the photolysis of sodium sulfide and sodium sulfide/sodium sulfite mixture without any photocatalyst. The findings of this study would be highly beneficial for the selection of sacrificial agents for a particular photocatalyst.