This study examines the electrochemical reforming of methanol for hydrogen production using novel DSA type anodes (modified with TiO2) with low metal loadings. Mass spectrometry (MS) in conjunction with electrochemical techniques were used to study the performance of the process as well as crossover phenomena. The electrolysis process was carried out in a Polymer Electrode Membrane (PEM) electrolyzer comprised of a Pt-Ru modified with TiO2 anode, a commercial Pt/C cathode, and a Nafion 117 electrolyte. Both methanol concentration and cell temperature were varied to investigate the cell performance. In all cases, our results showed that the Pt-Ru-TiO2 electrode had better electro-catalytic activity than the Pt-Ru electrode. This higher electro-catalytic activity of the TiO2-modified electrode was attributed to the enhanced Pt-Ru dispersion as well as the formation of smaller Pt and Ru particles, and thus to the higher electrochemical active surface. For all studied Membrane Electrodes Assemblies (MEAs), both CO2 and methanol crossover were observed at the cathode of the cell. In addition, it was found that hydrogen production is taking place with Faradaic efficiency values very close to 100%. This study demonstrates that the TiO2-modified electrode with a decreased noble-metal loading can increase the current density up to 56%.