The synergistic effects of titanium dioxide photocatalysis in combination with Fenton-like reactions for photoelectrochemical based hydrogen production and wastewater treatment is investigated in a newly designed photoelectrochemical reactor. Here, titanium dioxide nanoparticles are coated on the anode to enhance both hydrogen production and wastewater treatment processes. The reactor is tested under 600 W/m(2) of solar irradiance and is characterized using electrochemical, chemical oxygen demand, absorbance, and ultraviolet visible absorption spectroscopy techniques. The results show that the oxygen evaluation in the anolyte is substituted by iron(II)/iron(III) ions and the presence of hydrogen peroxide forms up the hydroxyl radicals via Fenton like process for degradation of organics in wastewater. While, hydrogen gas production in the catholyte is improved up to 8% by the means of proton reduction at the cathode in an acid medium. Also, 33% chemical oxygen demand removal efficiency of the synthetic textile wastewater (Reactive Black 5) is recorded in 17 h. This new hybrid configuration combines three different photo-assisted advanced oxidation processes such as ultraviolet/Fenton, ultraviolet/titanium dioxide, and ultraviolet/hydrogen peroxide with electrolysis process which increases hydrogen gas production rate and treats the wastewater.