In this work, we successfully synthesized CdS nanorods with a tunable morphology and structure by adjusting the composition of the solvent for the efficient production of H₂O₂via a two-channel pathway for photocatalytic water splitting under ambient conditions and organic electron donor free. The uniform nanorods of CdS provide a larger specific surface and a shorter charge transfer distance, which is beneficial for the separation of electron–hole pairs, thus having a great promotion effect on the increase of its H₂O₂ yield. Under ambient conditions and organic electron donor free, CdS nanorods achieve photocatalytic water splitting through the oxygen reduction reaction and water oxidation reaction with a high H₂O₂ yield of 1127 μmol h⁻¹ g⁻¹.