Fischer–Tropsch synthesis (FTS) was carried out in a water/oil mixture medium, using a Ru catalyst supported on a multi-walled carbon nanotube/MgO–Al2O3 hybrid as a catalyst support. The nanohybrid particles at the water/oil interface facilitated and stabilized the formation of water-in-oil emulsion, giving rise to an oil/emulsion/water trilayer liquid structure. FTS occurred at the emulsion phase with much higher conversion rates than those in oil single-phase reactions, yielding products with Anderson–Schulz–Flory distribution. Alkane-enriched hydrocarbons migrate to the top oil phase, while short alcohols remain in the bottom water phase. Thus, this multiphase liquid structure facilitates the separation of products according to their solubility in different phases. This significant advantage of combined reaction and separation is unique to the multiphasic system. In addition, differences in solubility could be used to enhance tolerance against impurities and catalyst poisons in the syngas feedstock. As...