The hydrogenation of CO over a RhVO4/SiO2 catalyst has been investigated after H-2 reduction at 773 K. A strong metal-oxide interaction (SMOI) induced by the decomposition of RhVO4 in H-2 enhanced not only the selectivity to C-2 oxygenates but also the CO conversion drastically, compared with an unpromoted Rh/SiO2 catalyst. The selectivity of the RhVO4/SiO2 catalyst was similar to those of conventional V2O5-promoted Rh/SiO2 catalysts (V2O5-Rh/SiO2), but the CO dissociation activity (and TOF) was much higher than for V2O5-Rh/SiO2, and hence the yield of C-2 oxygenates was increased.