The Li metal anode is regarded as the most potential electrode material in the next-generation energy storage system, because of the high energy density and specific capacity. However, the advancement of Li metal anode is restricted by the volume changing and dendrite growth. In this paper, the Co and Zn co-doped porous carbon framework (CF-CZ) derived from MOF structure was designed and produced to realize the dendrite-free Li metal anode. The porous structure could accommodate the deposited Li metal, which relaxes the pressure of electrode structure and relieves the volume changes. Meanwhile, the Co, Zn co-doping effectively improves the lithiophilicity of framework, which attracts Li+ and decreases the nucleation barrier. Besides, numerous micropores of MOF structure could divide the Li+ flux to reduce the local current density for dense sedimentation. With the synergies of co-doping and porous structure, the symmetric cell of CF-CZ shows better electrochemical performance (the overvoltage can be stable at 14 mV after 1200 cycles) than pure Cu foil, and the LFP cells deliver 116.4 mAh g−1 at 1 C after 200 cycles. As a consequence, the CF-CZ possesses the potential to be applied in Li metal anodes.