Screen‐printing is a commonly used method for the preparation of photoelectrodes. Although previous studies have explored the effect of the number of printed layers on the efficiency of dye‐sensitized solar cells, its interplay with the photoelectrocatalytic properties of the electrodes has rarely been examined. This study focuses on this issue by studying the photoelectrocatalytic oxidation of methanol over TiO2 electrodes. Incident photon‐to‐current efficiencies reached 87 % at the optimal conditions of monochromatic (338 nm) irradiation of one‐layer films at 0.2 V vs NHE. However, the irradiation wavelength and applied bias strongly influenced the relative behavior of the films. For instance, at 0.5 V and 327 nm irradiation, the one‐layer electrode was 6 times more efficient than the four‐layer one, while at 385 nm the four‐layer electrode was 3.5 times more efficient. The results were explained on the basis of differing light absorption properties and charge carrier lifetimes. Modelling and quantification of the electron diffusion length (5.7 μm) helped to explain why the two‐layer electrode (4.89 μm thick) showed the most consistent efficiencies across all conditions. Complementarily, transient absorption spectroscopy was used to correlate the thicknesses with charge carrier lifetimes. Electron transfer to FTO was apparent only for the thinner electrode. Our work shows that the optimization of photoelectrocatalytic processes should include the number of layers as a key variable.