tOrganic–inorganic hybrid electrolytes were prepared by co-hydrolysis and co-condensation of 3-glycidoxipropyltrimethoxysilane (GPTMS) and tetraethyl orthosilicate (TEOS) doped with lithium acetateas self-supported materials and thin-films. The effects of the relative molar content of LiAc on thephysicochemical properties of electrolytes, such as morphology, thermal, chemical and electrochemi-cal properties were investigated. Two and four probes test cells were designed for comparative studiesof ionic conductivity of hybrid electrolytes using electrochemical impedance spectroscopy (EIS). Similarionic conductivities were obtained using both measurement methods, reaching a maximum ionic conduc-tivity value of around 10−6S/cm at 25◦C. The conductivity mechanism presents Arrehenius behavior withthe increase of the temperature from 25◦C to 120◦C. The electrochemical stability window is found to bein the range of 0–5 V, which ensures that hybrid organic–inorganic materials are potential electrolytesfor solid-state rechargeable lithium ion batteries.