A catalytic process selectively produces ethanol by contacting synthesis gas (syngas), composed primarily of hydrogen and carbon monoxide, with three catalysts within a reactor. The first catalyst is a hydrogenation promoter comprising Cu--Zn, Mo or Fe with an optional alkali metal additive and an optional support of aluminum oxide, silica, zeolite or clay. The second catalyst is a homologation promoter comprising one or more of the Group VIII metals in free or combined form with a co-catalyst metals consisting of Y or lanthanide or actinide series metals with optional additives and support. The third catalyst is a hydrogenation promoter. This series of catalysts improves the selectivity and yield for ethanol from syngas.