Insufficient catalytic activity and stability of the present cathode materials inevitably hamper the industrial applications of solid oxide electrolysis cells (SOECs). Developing efficient cathodes is still a challenging task in the field of SOECs. This paper reports a novel non-perovskite-type cathode material with F doping (Fe₂TiO_5-δF_0.2) and without any alkaline earth elements. F doping increases the surface oxygen vacancies and improves the CO₂ adsorption capacity and conductivity of Fe₂TiO₅. The absence of alkaline earth elements avoids the formation of insulating and inactive carbonates during CO₂ electrolysis. It is worth noting that Fe₂TiO_5-δF_0.2 undergoes an ingenious phase transition during the electrolysis process, generating the heterogeneous Fe/FeTiO_3-δF_0.2 interface as the active center. The resulting cathode (Fe/FeTiO_3-δF_0.2) demonstrates good activity and stability for pure CO₂ electrolysis. The current density is close to 2.0 A cm⁻² at 1.6 V (850 °C) and the electrolysis voltage keeps near-constant during the 235 h galvanostatic test at 0.4 A cm⁻² (800 °C). The newly formed heterogeneous Fe/FeTiO_3-δF_0.2 microstructure is believed to be suitable for other catalytic processes.