The strategic combination of redox-active triazine- or quinoxaline-based lithium-ion battery (LIB) mechanisms with the polysulfide ring-mediated lithium-sulfur battery (Li-SB) mechanism enabled the configuration of covalent organic-framework (COF)-derived lithium-organosulfide (Li-OrSB) battery systems. Two vinylene-linked frameworks were designed by enclosing polysulfide rings via postsynthetic framework sulfurization, allowing for the separate construction of triazine-polysulfide and quinoxaline-polysulfide redox couples that can readily interact with Li ions. The inverse vulcanization of the vinylene linking followed by the sulfurization-induced nucleophilic aromatic substitution reaction (S_NAr) on the perfluorinated aromatic center of the COFs enabled the covalent trapping of cyclic-polysulfides. The experimentally observed reversible Li-interaction mechanism of these highly conjugated frameworks was computationally verified and supported by in situ Raman studies, demonstrating a significant reduction of polysulfide shuttle in a conventional Li-SB and opening the door for a COF-derived high-performing Li-OrSB.