Fe-based/CaO prepared by three different methods with various Ca and Fe precursors. Fe-Ca interactions in Fe-based/CaO during toluene steam reforming at 700 °C. Characterization before and after toluene steam reforming for evolution information. Fe-based/CaO activity depends on Fe2O3 presence and on Fe-Ca interactions stability. FeAc/CaO (M) best material for CO2 capture and α-Fe2O3 phase reducibility at 700 °C.