This study was aimed to evaluate the fundamentals for the purposeful preparation of Fe-based catalysts for CO2 conversion to higher hydrocarbons (C2+-hcs) with suppressed methane production. To this end tailored catalyst preparation and sophisticated material characterization by state-of-the-art techniques were combined with spatially resolved steady-state and transient kinetic analyses. To determine factors governing catalytic performance, the evolution of the microstructure and the phase composition of as-prepared iron oxides under CO2 Fischer-Tropsch synthesis conditions were established.