The shuttling of polysulfides on the cathode and the uncontrollable growth of lithium dendrites on the anode have restricted the practical application of lithium-sulfur (Li-S) batteries. In this study, a metal-coordinated 3D covalent organic framework (COF) with a homogeneous distribution of nickel-bis(dithiolene) and N-rich triazine centers (namely, NiS4-TAPT) was designed and synthesized, which can serve as bifunctional hosts for both sulfur cathodes and lithium anodes in Li-S batteries. The abundant Ni centers and N-sites in NiS4-TAPT can greatly enhance the adsorption and conversion of the polysulfides. Meanwhile, the presence of Ni-bis(dithiolene) centers enables uniform Li nucleation at the Li anode, thereby suppressing the growth of Li dendrites. This work demonstrated the effectiveness of integrating catalytic and adsorption sites to optimize the chemical interactions between host materials and redox-active intermediates, potentially facilitating the rational design of metal-coordinated COF materials for high-performance secondary batteries.