ZnO　with　good　lithiophilicity　has　widely　been　employed　to　modify　the　lithiophobic　substrates　and　facilitate　uniform　lithium　(Li)　deposition.　The　overpotential　of　ZnO-derived　Li　anode　during　cycling　depends　on　the　lithiophilicity　of　both　LiZn　and　Li2O　products　upon　lithiation　of　ZnO.　However,　the　striking　differences　in　the　lithiophilicity　between　Li2O　and　LiZn　would　result　in　a　high　overpotential　during　cycling.　In　this　research,　the　Al2O3/nZnO　(n　＞=　1)　hybrid　layers　were　precisely　fabricated　by　atomic　layer　deposition　(ALD)　to　regulate　the　lithiophilicity　of　ZnO　phase　and　Li2O/LiZn　configuration-determining　the　actual　Li　loading　amount　and　Li　plating/stripping　processes.　Theoretically,　the　Li　adsorption　energy　(E-a)　values　of　LiZn　and　Li2O　in　the　LiZn/Li2O　configuration　are　separately　predicted　as　-2.789　and　-3.447　eV.　In　comparison,　the　E-a　values　of　LiZn,　LiAlO2,　and　Li2O　in　the　LiZn/LiAlO2/Li2O　configuration　upon　lithiation　of　Al2O3/8ZnO　layer　are　calculated　as　-2.899,　-3.089,　and　-3.208　eV,　respectively.　Importantly,　a　novel　introduction　of　LiAlO2　into　the　LiZn/Li2O　configuration　could　enable　the　hierarchical　Li　plating/stripping　and　reduce　the　overpotentials　during　cycling.　Consequently,　the　Al2O3/8ZnO-derived　hybrid　Li-metal　anode　could　exhibit　electrochemical　performances　superior　to　these　of　ZnO-derived　Li　anode　in　both　symmetrical　and　full　cells　paired　with　a　LiNi0.6Co0.2Mn0.2O2　(NCM622)　cathode.