Lithium metal constitutes promising anode materials but suffers from dendrite growth. Lithiophilic host materials are highly considered for achieving uniform lithium deposition. Precise construction of lithiophilic sites with desired structure and homogeneous distribution significantly promotes the lithiophilicity of lithium hosts but remains a great challenge. In this contribution, a framework porphyrin (POF) material with precisely constructed lithiophilic sites in regard to chemical structure and geometric position is employed as the lithium host to address the above issues for dendrite-free lithium metal anodes. The extraordinary lithiophilicity of POF even beyond lithium nuclei validated by DFT simulations and lithium nucleation overpotentials affords a novel mechanism of favorable lithium nucleation to facilitate uniform nucleation and inhibit dendrite growth. Consequently, POF-based anodes demonstrate superior electrochemical performances with high Coulombic efficiency over 98%, reduced average voltage hysteresis, and excellent stability for 300 cycles at 1.0 mA cm-2, 1.0 mAh cm-2 superior to both Cu and graphene anodes. The favorable lithium nucleation mechanism on POF materials inspires further investigation of lithiophilic electrochemistry and development of lithium metal batteries.