Ethanol and higher alcohols are one of the most interesting alternatives to replace fossil fuels in the transportation sector. Nickel-modified alkali-doped molybdenum sulfide is a potential catalyst for the conversion of syngas to mixed alcohols. In this work, K-Ni-MoS2 catalysts were synthetized by coprecipitation in aqueous solution or in microemulsions, followed by alkali doping. The influence of the preparation route in CO hydrogenation was investigated at 91bar, 340/370°C and GHSV=2000–14,000NmL/hgcatalyst. The catalysts were also characterized by TGA, ICP, XPS, nitrogen adsorption, XRD, SEM-EDX and TEM. The novel microemulsion catalyst outperformed the conventional one, resulting in higher yields of ethanol and higher alcohols. The higher activity and selectivity was attributed to a higher concentration of promoters on the microemulsion catalyst surface, together with a lower degree of crystallinity.