Manganese and mixed vanadium oxides were prepared by the hydrolysis of acetylacetonates. They were characterized by different techniques, such as X-ray diffraction, XPS, temperature-programmed surface reaction (TPSR), and conversion and selectivity measurements. TPSR studies showed that H2O, CO2, and O2 are present in manganese oxide samples and that the ones containing vanadium desorb CO2, H2O, methanol, formaldehyde, O2. The vanadium-free catalysts and the ones with a lower vanadium content also exhibit high methanol conversion and selectivity to CO2 at higher temperatures. The selectivity to dimethyl ether is important in the catalyst without V at lower temperature. The greatest conversion at lower temperatures and the highest selectivities to CO2 are achieved with the catalysts having the highest vanadium content.