Chemical Looping Hydrogen (CLH) allows the direct production of pure hydrogen exploiting the redox properties of Fe, with high flexibility on the type of reductant used. In this work, a highly pure hydrogen stream suitable for the direct use into Proton Exchange membrane Fuel Cells was produced, using bioethanol as renewable fuel. The influence of both redox temperature (675°C–750 °C) and chemical composition of the Fe-based particles (2 wt% and 40 wt% of alumina added) on the carbon formation rate during reduction step was also deeply analyzed. Al2O3 changed both FexOy redox kinetics and equilibrium phases, leading to a complete iron deactivation at high Al2O3 concentration. The addition of an air oxidation step (3 steps CLH) is fundamental to restore the redox activity, with a constant efficiency of about 30% at 750 °C for 10 cycles. Furthermore, Al2O3 promotes the ethanol conversion into carbon, undermining the hydrogen purity.