Solid-state batteries (SSBs) that incorporate the argyrodite-Li 6 PS 5 Cl (LPSCl) electrolyte hold potential as substitutes for conventional lithium-ion batteries (LIBs). However, the mismatched interface between the LPSCl electrolyte and electrodes leads to increased interfacial resistance and the rapid growth of lithium (Li) dendrites. These factors significantly impede the feasibility of their widespread industrial application. In this study, we developed a composite electrolyte of the LPSCl/polymer to enhance the contact between the electrolyte and electrodes and suppress dendrite formation at the grain boundary of the LPSCl ceramic. The monomer, triethylene glycol dimethacrylate (TEGDMA), is utilized for in situ polymerization through thermal curing to create the argyrodite LPSCl/ polymer composite electrolyte. Additionally, the ball-milling technique was employed to modify the morphology and particle size of the LPSCl ceramic. The ball-milled LPSCl/polymer composite electrolyte demonstrates slightly higher ionic conductivity (ca. 2.21 × 10 −4 S/cm) compared to the as-received LPSCl/polymer composite electrolyte (ca. 1.65 × 10 −4 S/cm) at 25 °C. Furthermore, both composite electrolytes exhibit excellent compatibility with Li-metal and display cycling stability for up to 1000 h (375 cycles), whereas the asreceived LPSCl and ball-milled LPSCl electrolytes maintain stability for up to 600 h (225 cycles) at a current density of 0.4 mA/cm 2 . The SSB with the ball-milled LPSCl/polymer composite electrolyte delivers high specific discharge capacity (138 mA h/g), Coulombic efficiency (99.97%), and better capacity retention at 0.1C, utilizing the battery configuration of coated NMC811// electrolyte//Li-Indium (In) at 25 °C.