An all-solid-state battery represents a promising solution for overcoming current lithium-ion batteries ’technological and safety limitations. However, the individual limitations of both inorganic and organic solid electrolytes hinder technological progression. Hybrid solid electrolytes hold the potential to surpass these limitations by integrating both the inorganic and organic phases. A comparative assessment was conducted between hybrid solid electrolytes produced via solvent and dry synthesis, to address potential solvent interactions during hybrid solid electrolyte production and prioritise sustainability. At 30°C, the comparative analysis demonstrates that the dry-processed PEO13LPSC10 hybrid solid electrolyte achieves a higher ionic conductivity of 1.61×10−5 S/cm, exceeding that of its solvent pro-cessed counterpart, which exhibits a conductivity of 1.51×10−5 S/cm. Conversely, for the PEO18LPSC10 hybrid solid electrolytes, the solvent processing method leads to a higher ionic conductivity, measured at 8.37×10−6 S/cm, in contrast to 7.61×10−6 S/cm observed for the dry-processed method. Thermal analysis indicates that heating above the polymer’s melting transition temperature leads to slow crystallisation in hybrid solid electrolytes using the dry method, resulting in two crystalline phases, as opposed to the single crystalline phase, which was observed using the solvent method. Both processing methods demonstrate homogeneity when comparing the top and bottom surfaces; however, an analysis of surface compositions between the two synthesis methods reveals distinct differences, as identified through. X-ray photoelectron spectroscopy. Moreover, decomposition is observed in both synthesis approaches but is more significant in solvent synthesis. The chemical stability of hybrid solid electrolytes produced by dry synthesis surpasses the solvent-based method. Further analysis through the dry method investigation reveals that an ethylene oxide to Li+ ratio of 10:1, and a Li6PS5Cl ratio of 10 wt%, yield the highest ionic conductivity among all studied hybrid solid electrolytes. This combination achieves an ionic conductivity of 3.35×10−5 S/cm at 30° C. Additionally, adding Li6PS5Cl and the alkali salt lithium bis(trifluoromethanesulfonyl)imide enhances the amorphous nature and mobility of the polymer, due to a plasticising effect on the organic matrix.