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These low\u2010resistance pathways promote directional lithium\u2010ion (Li\n                    <jats:sup>+<\/jats:sup>\n                    ) migration through a narrower, more spatially ordered distribution of coordination environments, achieved via site\u2010to\u2010site hopping and\/or guest\u2010assisted vehicular motion within the channels. This review presents a design\u2010oriented framework linking COF structural descriptors to ion\u2010transport metrics through a cause\u2010effect\u2010performance relationship. We first summarize the Li\n                    <jats:sup>+<\/jats:sup>\n                    transport mechanism in confined COF channels, covering site\u2010to\u2010site hopping along pore walls and guest\u2010assisted vehicular motion in filled channels. We then correlate (i) topology and channel architecture, (ii) pore\u2010wall chemical functionality and framework charge, (iii) crystallinity, stacking registry, and channel alignment, and (iv) hybrid COF architectures with performance indicators including ionic conductivity (\u03c3), activation energy (Ea), lithium\u2010ion transference number (tLi\n                    <jats:sup>+<\/jats:sup>\n                    ), transport anisotropy, and effective conductivity in working membranes (\u03c3eff). Through representative case studies, we highlight cases where high intrinsic channel transport does and does not translate into device\u2010relevant \u03c3eff. Finally, we propose standardized reporting practices and device\u2010level benchmarks to accelerate the shift from empirical materials discovery toward predictive ion\u2010highway engineering for next\u2010generation solid\u2010state lithium batteries.\n                  <\/jats:p>","DOI":"10.1002\/smll.75286","type":"journal-article","created":{"date-parts":[[2026,8,25]],"date-time":"2026-08-25T12:12:58Z","timestamp":1787659978000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Covalent Organic Framework Electrolytes for Solid\u2010State Lithium Batteries: Designing Ion Highways for Next\u2010Generation Energy Storage"],"prefix":"10.1002","volume":"22","author":[{"given":"Rajesh","family":"Dhanushkotti","sequence":"first","affiliation":[{"name":"Department of Chemical and Materials Engineering Concordia University  Montreal Quebec Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-1239-8813","authenticated-orcid":false,"given":"Ningaraju","family":"G. 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