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Anode‐free Li metal batteries (AFLMBs) are highly advantageous due to their high energy density, low cost, and simple fabrication. However, severe challenges, such as uncontrolled dendrite formation and low coulombic efficiency, restrict their practical application. Herein, this work introduces a silver nanoparticles incorporated p‐doped conjugated polymer (Ag‐PCP) wetting agent on the copper current collector, which promotes both uniform Li nucleation and rapid formation of a LiF‐rich solid electrolyte interphase (SEI) at the early stage, resulting in interfacial stabilization and high Li utilization efficiency. Moreover, this work verifies the interfacial fluorinated mechanism of the Ag‐PCP to efficiently achieve a favorable SEI chemistry, which serves as an intermediate process for promoting LiF formation. Benefiting from the synergistic effect of Ag–Li alloying and F‐doping chemistry of the Ag‐PCP chains, the deposited Li exhibits a compact column‐like structure with dendrite‐free morphology, and the anode‐free cells display superior cycling stability with long lifespan even under harsh conditions, with the LFP//Ag‐PCP│Cu full cell having a high capacity retention of 72% (Li inventory retention rate, 99.8%) at 1 C‐rate after 200 cycles. [ABSTRACT FROM AUTHOR]