A new type of highly conductive organic-inorganic hybrid polymer electrolytes has been synthesized by the reaction of poly(propylene glycol)block-poly(ethylene glycol)block-poly(propylene glycol) bis(2-aminopropyl ether), 2,4,6-trichloro-1,3,5-triazine and alkoxysilane precursor 3-(glycidyloxypropyl)trimethoxysilane, followed by doping of LiClO4. The C-13 and Si-29 solid-sate NMR results confirm the successful synthesis of the organic-inorganic hybrid structure. The solid hybrid electrolyte thus obtained exhibits a maximum ionic conductivity of 1.6 x 10(-4) S cm(-1) at 30 degrees C, which is the highest among the organic-inorganic hybrid electrolytes. The hybrid electrolytes are electrochemically stable up to 4.2 V. The prototype electrochromic device with such a solid hybrid electrolyte demonstrates a good coloration efficiency value of 183 cm(2) C-1 with a cycle life over 200 cycles. For the lithium-ion battery test, the salt free solid hybrid membrane is swelled with a LiPF6-containing electrolyte solution to reach an acceptable ionic conductivity value of 6.5 x 10(-3) S cm(-1) at 30 degrees C. The battery cell carries an initial discharge capacity of 100 mAh g(-1) at 0.2C-rate and a coulombic efficiency of about 95% up to 30 cycles without the sign of cell failure. The present organic-inorganic hybrid electrolytes hold promise for applications in electrochromic devices and lithium ion batteries. (C) 2014 Elsevier B.V. All rights reserved.