Li-Argyrodite　solid　electrolytes　have　shown　potential　for　developing　high　energy　density　and　safe　all-solid-state　lithium　metal　batteries　(ASSLMBs)　due　to　the　high　ionic　conductivity　and　ductile　mechanical　property.　However,　the　incompatibility　of　the　electrolyte　with　lithium　anode　due　to　the　redox　decomposition　of　PS43−　tetrahedrons　inhibits　its　further　application　in　ASSLMBs.　Herein,　the　redox　behavior　is　manipulated　by　orbital　hybridization　induced　electronic　structure　reconfiguration　through　in-situ　electrochemical　(de)lithiation　of　Li5.5PS4.5Cl1.5.　The　optimized　electrolyte　with　new　s-p　hybridization　of　Li-Mg　and　Mg-S　and　p-p　hybridization　of　P-S-O　not　only　manipulates　the　electrons　acceptance　of　PS43-　tetrahedrons,　but　also　induces　new　electron-shielding　and　lithiophilic　phases.　The　optimized　electrolyte　therefore　shows　superior　cycling　stability　of　above　2000　h　at　0.2　mA　cm−2　with　symmetrical　lithium　electrodes.　The　all-solid-state　batteries　with　LiFePO4　and　LiNi0.83Co0.12Mn0.05O2　as　cathode　display　stable　cycle　performance　of　500　and　200　cycles,　respectively.　This　work　gains　insights　into　the　manipulating　mechanism　for　the　redox　behavior　of　Li-argyrodite　electrolyte　through　orbital　hybridization,　and　opens　a　new　route　for　addressing　the　lithium　anode　integration　issue　of　ASSLMBs　with　high　energy　density　and　safety.　©　2025　Elsevier　B.V.