Aluminium is one of the promising alternative anode materials due to its high specific capacity. However, some critical problems seriously limit its practical applications, such as the low coulombic efficiency and poor cycle performance resulting from the huge volume change during cycling. Herein, a novel poly(furfuryl alcohol)/carbon black binder composite is coated on the surface of aluminium foil as a robust and conductive protective‐layer in order to maintain the integrity of the hybrid aluminium anode. The results show 150 cycles under the pre‐set cut‐off capacity loading of 400 mA·h·g‐1 is obtained, and exhibits obvious advantages over a bare aluminium anode, which will crack after just 25 cycles. For full‐cell testing paired with LiFePO4 cathode, the cell using hybrid aluminium anode has a better capacity retention against the unprotected aluminium anode. The proposed PFA‐based strategy offers a new electrode process, with the advantages of being low cost, environmentally benign and solvent free to industrial applications.