Ethanol is prepared with high selectivity by the catalytic reaction of carbon monoxide and hydrogen. The catalyst composition comprises:(A) catalyst component consisting of(a) a rhodium component,(b) a lithium component, and(c) a component of at least one element selected from the group consisting of iridium, manganese, scandium, mangesium, yttrium, ytterbium, lutecium, vanadium and chromium; and(B) catalyst component, which is supported on a separate carrier from said (A) catalyst component, being selected from the group consisting of(a) an iron component and a component of at least one element selected from the group consisting of iridium and palladium,(b) a molybdenum component and a component of at least one element selected from the group consisting of iridium and palladium,(c) an iron component, a molybdenum component and a component of at least one element selected from the group consisting of iridium and palladium, and(d) a copper component and optionally a component of at least one element selected from the group consisting of zinc and chromium.