TiO2 nanoparticles exhibit good photocatalytic activity for hydrogen evolution through water splitting; however, they demonstrate weak activity under visible light irradiation due to the wide band gap of TiO2. Deposition with noble metals such as platinum, as cocatalyst, led to the red-shift of the absorption edge of rutile TiO2; however, its activity is not significant for the photoelectrochemical (PEC) degradation of azo dyes such as methyl orange (MO). Herein, we investigated the photoelectrocatalytic degradation reaction of MO in a PEC cell based on Pt-deposited TiO2 thin film. The performance of the cell increased through the formation of mesoporous coral-like structures with sub-2 nm pores and the formation of defect states on the electrode surface. UV-vis studies confirmed, when methanol was added, the PEC cell exhibited a much higher MO degradation efficiency (99.6% after 28 min UV irradiation) than in the absence of methanol (64.7%). GC-MS studies confirmed the oxidation of methanol to formaldehyde, reacting on the electrode surface, followed by the reduction of the protons into hydrogen over the Pt sites. Also, the conversion of formaldehyde to formic acid and formic acid to CO2 are possible mechanisms to increase the hydrogen evolution rate to 418 mu mol/h under visible light irradiation. Reaction of adsorbed active species within the surface of coral-like TiO2 structures with sub-2 nm pores provides high activity of the proposed PEC cell for visible-light-driven water splitting. These research studies may be continued to the design of other efficient semiconductor photocatalysts.