The safety problem caused by lithium dendrite of lithium metal anode and the rapid capacity decay problem caused by the shuttle effect of polysulfide and polyselenide during the charge and discharge of selenium disulfide cathode limit the application of lithium selenium disulfide batteries significantly. Here, a fibrous ATFG-COF, containing rich carbonyl and amino functional groups, was applied as the separator coating layer. Density Functional Theory (DFT) theoretical calculations and experimental results showed that the abundant carbonyl group in ATFG-COF had a positive effect on lithium ions, and the amino group formed hydrogen bonds with bis ((trifluoromethyl) sulfonyl) azanide anionics (TFSI−), which fixed TFSI− in the channel, so as to improve the transfer number of lithium ions and narrow the channels. Therefore, ATFG-COF fiber coating can not only form a rapid and uniform lithium-ion flow on the lithium anode to inhibit the growth of lithium dendrites, but also effectively screen polysulfide and polyselenide ions to suppress the shuttle effect. The Li-SeS2 cell with ATFG-COF/polypropylene (ATFG-COF/PP) separator exhibited good cycle stability at 0.5 C and maintained a specific capacity of 509 mAh/g after 200 cycles. Our work provides insights into the design of dual-function separators with high-performance batteries.