Fischer‐Tropsch synthesis (FTS) is an attractive opportunity to prepare fuels and chemicals, avoiding fossil resources exploration. Co2C was recently demonstrated to exhibit outstanding properties in Fischer‐Tropsch to olefins (FTO) reaction, inhibiting methane formation. However, the exact mechanisms have not been entirely revealed yet. Here we are proposing a study combining DFT calculations and microkinetic modelling (MKM) in order to unveil the dominant reaction pathways of three products of interest in FTS, namely methane, ethylene, and methanol, over (020), (101) and (111) facets of Co2C. We found methane and ethylene share the same determining states, being responsible for the competition between the two species. Since our MKM gives results suggesting the surface is fully covered with CO at the steady‐state, we expect that including adsorbate‐adsorbate interactions both in DFT calculations and MKM simulations would be important in the future studies of FTS over Co2C surfaces.