The research team at the Dalian Institute of Chemical Physics, part of the Chinese Academy of Sciences, has made significant strides in the development of key materials for high-specific-energy all-solid-state batteries. The team introduced an innovative inorganic-phase-induced in-situ chemical reconstruction approach for organic phases, leading to the creation of a novel organic-inorganic composite solid-state electrolyte material. This method leverages the Lewis base active sites on the surface of lithium chloroxide to trigger in-situ defluorination of polyvinylidene fluoride (PVDF), resulting in the formation of unsaturated carbon-carbon double bond structures. This transformation strengthens the organic-inorganic interface through robust chemical bonding, establishing a continuous lithium-ion conduction pathway with minimal transport energy barriers. This integration capitalizes on the strengths of both inorganic materials and polymers. The PVDF-Li3OCl composite solid-state electrolyte, crafted based on this strategy, demonstrates excellent electrochemical performance, mechanical stability, and single-ion conduction properties. When utilized in an NCA ternary solid-state battery along with its separator, the battery can achieve 350 stable cycles at a 1C rate, maintaining a capacity retention rate of 84.2%. This breakthrough offers a promising new avenue for enhancing the cycle life of solid-state batteries.