Safety issues in Li-ion battery system have been prime concerns, as demands for power supply device applicable to wearable device, electrical vehicles and energy storage system have increased. To solve safety problems, promising strategy is to replace organic liquid electrolyte with non-flammable solid electrolyte, leading to the development of all-solid-state battery. However, relative low conductivity and high resistance from rigid solid-solid interface hinder a wide application of solid electrolyte. Composite electrolytes composed of organic and inorganic parts could be alternative solution, which in turn bring about the increase of conductivity and conformal contact at physically rough interfaces. In our study, composite electrolytes were prepared by combining poly(ethylene oxide)(PEO) and Li7La3Zr2O12 (LLZO). The crystallinity, morphology and electrochemical performances were investigated with the control of LLZO contents from 0 wt% to 50 wt%. From the results, it is concluded that optimum content and uniform dispersion of LLZO in polymer matrix are significant to improve overall conductivity of composite electrolyte.