Li　metal　has　been　considered　as　a　potential　anode　candidate　for　next‐generation　high‐energy　Li‐metal　batteries,　even　though　the　uncontrollable　growth　of　Li　dendrites　shortens　their　cycling　lifespan.　Herein,　a　reliable　and　dendrite‐free　Li‐metal　anode　is　fabricated　via　inducing　chemical　confinement　based　on　an　atomic　layer　deposited　lithiophilic　ZnO　in　situ　generating　LiZn/Li2O　arrays.　In　a　configuration,　the　arrays　consisting　of　uniformly　distributed　LiZn　and　Li2O　phases,　the　lithiophilic　Li2O　phases　with　favorable　Li　diffusion　barrier　guarantee　the　preferential　Li　nucleation　and　prevent　the　Li　diffusion　to　some　sites　with　uneven　charge　accumulation.　Furthermore,　these　functional　LiZn/Li2O　configurations　with　satisfied　localized　free　electron　distribution　can　effectively　decompose　the　Li　clusters　to　prevent　Li　aggregation.　Meanwhile,　the　electron‐conductive　LiZn　phases　ensure　efficient　electron　transfer　throughout　the　configuration.　Therefore,　the　LiZn/Li2O‐derived　chemical　confinement　enables　uniform　Li　deposition.　Consequently,　the　as‐prepared　Li‐metal　anode　presents　an　overpotential　＜45 mV　at　15 mA　cm−2　in　the　symmetrical　cells.　Moreover,　the　preferable　cycling　stability　and　rate　capability　are　delivered　by　the　as‐assembled　cells　with　a　LiNi0.6Co0.2Mn0.2O2　(NCM622)　cathode.　It　is　believed　that　the　strategy　proposed　here　can　be　also　beneficial　to　other　effective　chemical　confinement　systems　for　fabricating　high‐performance　Li　metal　anode.