In this study, polyetheramine and polyetherdiamine were cross-linked separately with (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and poly(ethylene glycol) diglycidyl ether (PEGDGE) and then blended in different ratios to obtain blended hybrid solid polymer electrolytes (SPEs). The blend network architecture improved the LiClO4 salt dissociation, which led to a higher ionic conductivity of the SPEs (4.5 × 10−4 S cm−1 at 60 °C and 1.2 × 10−4 S cm−1 at 30 °C for the [O]/[Li] ratio of 16). When the salt concentration was increased, the phase of the SPEs changed from semi-crystalline to an amorphous state, as revealed by differential scanning calorimetry. Complexation with different constituents of the SPEs was evidenced from the Fourier transform infrared measurements, while 13C and 29Si solid-state NMR spectroscopy provided information about the successful formation of the blend organic-inorganic hybrid with a silicate architecture, and 7Li NMR static linewidth measurements gave an insight into the dynamic behaviour of the lithium ions inside the SPEs. The blend hybrid SPEs demonstrated an electrochemical stability window of over 5 V. The electrochemical performance of the blend hybrid SPE assembled in a battery with lithium as the anode and LiFePO4 as the cathode exhibited a good cycle life of over 100 cycles, with an initial discharge capacity of 110 mA h g−1 and a coulombic efficiency of over 99%. With these good characteristic properties, the present blend hybrid SPE has the potential to be used in lithium solid-state batteries and other electrochemical devices.