TiO2 nanotube membranes (TNM) were synthesized, separated (by electrochemical anodization) and modified with Pt-Ru electrocatalyst to assess their photoelectrocatalytic activity towards methanol (MeOH) oxidation. The feasibility of use of these composite materials was evaluated in different supports to observe the development of the electrochemical responses as a function of the nature of the electrical collecting substrate. The results suggested that, while the Pt-Ru decorated TMN present photoelectrocatalytic activity, the electrical contact in the back might be the limiting step in current collection. Such findings were demonstrated by performing scanning electrochemical microscopy SECM over the surface of the TNMs, where methanol was oxidized in the microelectrode tip of the SECM. This approach corroborated the suitability of TNMs to be modified with an electrocatalyst and its application in current technology such as microfluidic fuel cells.