A stable anode‐free all‐solid‐state battery (AF‐ASSB) with sulfide‐based solid‐electrolyte (SE) (argyrodite Li 6PS 5Cl) is achieved by tuning wetting of lithium metal on “empty” copper current‐collector. Lithiophilic 1 µm Li 2Te is synthesized by exposing the collector to tellurium vapor, followed by in situ Li activation during the first charge. The Li 2Te significantly reduces the electrodeposition/electrodissolution overpotentials and improves Coulombic efficiency (CE). During continuous electrodeposition experiments using half‐cells (1 mA cm −2), the accumulated thickness of electrodeposited Li on Li 2Te–Cu is more than 70 µm, which is the thickness of the Li foil counter‐electrode. Full AF‐ASSB with NMC811 cathode delivers an initial CE of 83% at 0.2C, with a cycling CE above 99%. Cryogenic focused ion beam (Cryo‐FIB) sectioning demonstrates uniform electrodeposited metal microstructure, with no signs of voids or dendrites at the collector‐SE interface. Electrodissolution is uniform and complete, with Li 2Te remaining structurally stable and adherent. By contrast, an unmodified Cu current‐collector promotes inhomogeneous Li electrodeposition/electrodissolution, electrochemically inactive “dead metal,” dendrites that extend into SE, and thick non‐uniform solid electrolyte interphase (SEI) interspersed with pores. Density functional theory (DFT) and mesoscale calculations provide complementary insight regarding nucleation‐growth behavior. Unlike conventional liquid‐electrolyte metal batteries, the role of current collector/support lithiophilicity has not been explored for emerging AF‐ASSBs.