CO hydrogenation over Mn promoted Rh/NaY catalysts was studied at 10 bar and 250-degrees-C. Significant selectivity to oxygenates, mainly ethanol and ethyl acetate, was obtained after neutralizing the protons that are formed during reduction of Rh ions. Layered bed experiments show that protons act as sites catalyzing secondary reactions. Protons also convert Mn(OH)2 to Mn2+ ions; the catalysts with highest selectivity to oxygenates contain MnO particles and Rh clusters. The results suggest chemical interaction of adsorbates on Rh(n) clusters with those on MnO.