AbstractThe production of liquid hydrocarbons from syngas (CO and H₂) via the combined Fischer‐Tropsch (FT) synthesis and hydroprocessing (HP) is a promising strategy to provide valuable chemicals and fuels based on renewable feedstocks. High yields of liquid products are essential for industrial implementation since short‐chain side products like methane and CO₂ reduce the overall carbon efficiency, which holds true especially for bi‐functional Co/zeolite catalysts. In order to investigate the influence of the support material properties on the methane and CO₂ selectivities in the combined FT and HP reaction, we synthesized four well‐defined catalyst materials with similar cobalt particle sizes. The active material is supported on either meso‐ or microporous silicates or aluminosilicates. The catalytic properties are investigated in FT experiments at industrially relevant conditions (20 bar, 200–260 °C) and correlated with in situ x‐ray absorption spectroscopy results to determine the chemical environment responsible for the selectivity observed. The origin of the high methane selectivity detected for crystalline and amorphous aluminosilicate was mainly traced back to the strong cobalt‐support interactions. The high CO₂ selectivity, observed only for crystalline zeolite materials, is driven by the presence of oxidized cobalt species, while the acidic support in combination with micropores and possible overcracking leads to the observed drop in the C₅₊ selectivity.