Methane fed TiO2/RuO2/PTFE gas diffusion electrodes (GDEs) have been used for the electrosynthesis of methanol in 0.1 mol L -1 of Na2SO4 supporting electrolyte. By-products such as formaldehyde and formic acid are usually also formed during electrolyses, with the latter formed at a similar rate as that of methanol. In this study, V2O5 was added to the composition of the GDE to improve its selectivity for methanol. TiO2/RuO2/V 2O5 powder hot-pressed with PTFE resulted in a GDE suitable for oxidative electrosynthesis with simultaneous oxygen evolution. By feeding the TiO2/RuO2/V2O5/PTFE GDE with methane, it was possible to enhance its selectivity for methanol at low values of current density. Furthermore, the formation of formic acid and formaldehyde was suppressed, allowing for higher current efficiencies. The addition of 5.6% of V2O5 increased the electrode's current efficiency to 57% at 2.0 V, which is 2-fold higher than the efficiency achieved in the absence of vanadium oxide. © 2012 Elsevier Ltd.87 606610Rocha, R.S., Amargo, L.M.C., Lanza, M.R.V., Bertazzoli, R., A Feasibility Study of the Electro-recycling of Greenhouse Gases: Design and Characterization of a (TiO2/RuO2)/PTFE Gas Diffusion Electrode for the Electrosynthesis of Methanol from Methane (2010) Electrocatalysis, 1, p. 224Rocha, R.S., Lanza, M.R.V., Bertazzoli, R., Electrosynthesis of Ethylene Glycol from Oxidation of Ethylene Using a TiO2-RuO2/PTFE Gas Diffusion Electrode (2011) Electrocatalysis, 2, p. 273Fóti, G., Gandini, D., Comninellis, Ch., Anodic oxidation of organics on thermally prepared oxide electrodes (1997) Current Topics in Electrochemisty, 5, p. 71Rocha, R.S., V, M.R., Lanza, Bertazzoli, R., (2011) Electrochemical Process of Synthesis Os Alcohols Using Gas Diffusion Electrodes, , BR Patent PI 1102137-3Rocha, R.S., V, M.R., Lanza, Bertazzoli, R., (2011) Gas Diffusion Electrode, Process for Obtaining Gas Diffusion Electrodes and Their Uses, , BR Patent PI 1102984-6Sen, A., Benvenuto, M.A., Lin, M., Hutson, A.C., Basickes, N., Activation of methane and ethane and their selective oxidation to the alcohols in protic media (1994) Journal of the American Chemical Society, 116, p. 998Chen, L., Yang, B., Zhang, X., Dong, W., Cao, K., Zhang, X., Methane Oxidation over a V2O5 catalyst in the liquid phase (2006) Energy & Fuels, 20, p. 915Forti, J.C., Rocha, R.S., Lanza, M.R.V., Bertazzoli, R., Electrochemical synthesis of hydrogen peroxide on oxygen-fed graphite/PTFE electrodes modified by 2-ethylanthraquinone (2007) Journal of Electroanalytical Chemistry, 601, p. 63Galizzioli, D., Tantardini, F., Trasatti, S., Ruthenium dioxide: A new electrode material. I. Behaviour in acid solutions of inert electrolytes (1974) Journal of Applied Electrochemistry, 1, p. 57De Faria, L.A., Boodts, J.F.C., Trasatti, S., Physico-chemical and electrochemical characterization of Ru-based ternary oxides containing Ti and Ce (1992) Electrochimica Acta, 37, p. 2511Lassali, T.A.F., Boodts, J.F.C., De Castro, S.C., Landers, R., Trassati, S., UHV and electrochemical studies of the surface properties of Ru+Pt+Ti mixed oxide electrodes (1994) Electrochimica Acta, 39, p. 95Pelegrino, R.R.L., Vicentin, L.C., De Andrade, A.R., Bertazzoli, R., Thirty minutes laser calcination method for the preparation of DSA® type oxide electrodes (2002) Electrochemistry Communications, 4, p. 139Liu, A., Ichihara, M., Honma, I., Zhou, H., Vanadium-oxide nanotubes: Synthesis and template-related electrochemical properties (2007) Electrochemistry Communications, 9, p. 1766Guerra, E., Ciuffi, K.J., Oliveira, H.P., V2O5 xerogel-poly(ethylene oxide) hybrid material: Synthesis, characterization, and electrochemical properties (2006) Journal of Solid State Chemistry, 179, p. 3814