Abstract: The generation of hydrogen (H2) by semiconductor-based photocatalysis is seen as cost-effective and environmentally advantageous. Nevertheless, insufficient photon absorption and rapid recombination of photon-induced charge (e-/h+) pairs significantly hinder the practical application of this method for hydrogen production. This research aimed to produce hydrogen (H2) while removing contaminants from refinery wastewater by photocatalytic oxidation augmented by laser stimulation, concentrating on the creation of two photoanodes for Total Organic Carbon (TOC) reduction in refinery wastewater. The exploitation of the band gap between two substrates to improve the absorption of rutile TiO2/α-Fe2O3 photocatalysts in the UV and visible spectra resulted in a significant enhancement in TOC removal rates, reaching 96%. The hydrogen generation rate was 7960 μmol/L, and the solar-to-hydrogen (STH) efficiency for hydrogen production was 86.92% for pollutant removal, observed under optimal reaction conditions of pH 3, 40C°, a reaction duration of 50 minutes, and a catalyst dosage of 0.4 mg/Lcm², illuminated by a combination of (473+532+632) nm laser and UV source. This study illustrates that rutile TiO2/α-Fe2O3 catalysts serve as innovative photoanodes for effective total organic carbon (TOC) removal and green hydrogen production using photoelectrochemical (PEC) processes, representing the most environmentally sustainable option. possessing considerable potential for advancement in particular applications for refinery wastewater treatment.