<p>Solid-state lithium metal batteries have emerged as a highly promising energy storage technology, owing to their exceptional safety profile and remarkable energy density. Nevertheless, their widespread commercialization has been substantially impeded by the intrinsic limitations of solid-state electrolytes, particularly their inadequate Li⁺ conductivity and unsatisfactory interfacial stability. To address these critical challenges, the development of advanced solid-state electrolytes featuring highly selective and rapid Li⁺ transport pathways represents a pivotal strategy with substantial application prospects. In this study, we investigate an innovative solid-state electrolyte system based on covalent organic frameworks (COFs) with dimethyl modification and C–N bond linkage as the donor, which demonstrates exceptional capability in modulating the Li⁺ coordination environment, facilitating ion migration, providing continuous transport channels, and ultimately enhancing Li⁺ conductivity. The D-A COF-based solid-state electrolyte exhibits superior electrochemical performance, achieving an impressive Li⁺ conductivity of 1 × 10⁻³ S/cm and demonstrating exceptional cycling stability (1500 h) in Li∣Li symmetric cells. Comprehensive characterizations employing <i>in-situ</i> techniques and molecular dynamics simulations reveal that the abundance of electron donors plays a crucial role in enhancing the kinetics of Li⁺ transport. These findings provide a robust foundation for the rational design and fabrication of highperformance COF-based solid-state electrolytes, potentially paving the way for next-generation energy storage systems.</p>