Alcohol electrolysis using polymeric membrane electrolytes is a promising route for storing excess renewable energy in hydrogen, alternative to the thermodynamically limited water electrolysis. By properly choosing the ionic agent (i.e. H+ or OH) and the catalyst support, and by tuning the catalyst structure, we developed membrane-electrode-assemblies which are suitable for cost-effective and efficient alcohol electrolysis. Novel porous electrodes were prepared by Atomic Layer Deposition (ALD) of Pt on a TiO2-Ti web of microfibers and were interfaced to polymeric membranes with either H+ or OH conductivity. Our results suggest that alcohol electrolysis is more efficient using OH conducting membranes under appropriate operation conditions (high pH in anolyte solution). ALD enables better catalyst utilization while it appears that the TiO2-Ti substrate is an ideal alternative to the conventional carbon-based diffusion layers, due to its open structure. Overall, by using our developmental anodes instead of commercial porous electrodes, the performance of the alcohol electrolyser (normalized per mass of Pt) can be increased up to ~30 times.