Future energy storage could be distributed at local plants and involve production of methanol from reaction of sustainably derived hydrogen with CO or CO2 from locally available carbon sources. Such decentralized production would benefit from milder operating conditions than found in the current large-scale industrial process. We propose that a route via CO hydrogenation deserves consideration for this purpose, as it will be free of water, which is unavoidable from CO2-containing gas and strongly inhibiting to the methanol synthesis at lower temperatures. On pure Cu the rate of methanol synthesis from CO is an order of magnitude lower than the rate from CO2, but active CO hydrogenation catalysts can emerge from a bifunctional mechanism in catalysts that combine copper with a basic oxide. Mechanistic studies are consistent with the bifunctional Cu/support synergy arising from a mechanism, where basic oxide sites activate CO as formates at the metal/oxide interface followed by metal assisted hydrogenation of the interfacial formates. Active catalysts for CO hydrogenation are strongly inhibited by CO2, which forms carbonates that block the basic oxide sites and thereby prevent the synergistic pathway from CO. Graphic