In this study, polysiloxane and polyetherdiamine based comb-shaped solid polymer electrolytes (SPEs) are developed by hydrosilylation and sol-gel reactions of polymethylhydrosiloxane, allyltriethoxysilane, bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol and (3-glycidoxypropyl) trimethoxysilane followed by LiClO4 doping. The absence of residual Si-H functionality in FTIR and Si-29 CPMAS NMR spectra confirms the completion of hydrosilylation reaction. The formation of comb-shaped SPEs with silicate backbones is confirmed by C-13 and Si-29 solid-state NMR spectroscopy. The maximum ionic conductivity value of 5.8 x 10(-4) S cm(-1) is obtained for the SPE with [O]/[Li] ratio of 16 at 80 degrees C with electrochemical stability window reaching up to 4.8 V. The fabricated electrochromic device with the hybrid SPE of [O]/ [Li] = 16 demonstrates good electrochromic contrast and optical density change values of 49.3% and 0.39, respectively, at wavelength of 550 nm. The results show that the present comb-shaped SPEs have potential to be used in various electrochemical devices.