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The practical application of solid‐state lithium‐metal batteries (SSLMBs) based on polymer solid electrolytes has been hampered by their low ion conductivity and lithium‐dendrite‐induced short circuits. This study innovatively introduces 1D ferroelectric ceramic‐based Bi4Ti3O12‐BiOBr heterojunction nanofibers (BIT‐BOB HNFs) into poly(ethylene oxide) (PEO) matrix, constructing lithium‐ion conduction...