Ag-Rh/SiO2 catalysts which exhibit activity and selectivity for oxygenate and hydrocarbon synthesis have been characterized by X-ray diffraction (XRD). XRD patterns show that the catalysts prepared using Rh chloride precursor contain Rh, Ag, AgCl, and AgClO2 crystallites. The size of these crystallites varied with the amount of Ag in the catalyst. The variation in crystallite size of Rh, Ag, AgCl, and AgClO2 with Ag/Rh ratio has an impact on the activity and selectivity for synthesis of oxygenates and hydrocarbons during CO hydrogenation and ethylene hydroformylation reactions. The selectivity towards oxygenates is decreased on the Ag-Rh catalysts due to the presence of AgCl and AgClO2 crystallites on the catalyst surface. Ag-Rh catalyst with Ag/Rh ratio of 0.5 gives a higher activity and selectivity for ethanol and propanol during CO hydrogenation and ethylene hydroformylation than the other Ag-Rh catalysts. Ag-Rh catalysts prepared from Rh chloride and Ag nitrate precursors are less active and selective for oxygenate synthesis than those prepared from nitrate precursors. Ag-Rh catalysts for oxygenate synthesis should be prepared using nitrate precursors.