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Polyethylene oxide (PEO) is a polymeric material that has been widely used as solid polymer electrolytes (SPEs) for all-solid lithium ion battery (LIB) due to its excellent chemical stability. However, its low ionic conductivity at room temperature can be a significant problem that hampers the performance of the LIBs. Polyvinyl alcohol (PVA), due to its amorphous structure, is one of the polymers that is expected to improve the ionic conductivity of SPEs. In this study, we added polyvinyl alcohol (PVA) as a composite polymer to PEO based SPEs, with a varied amount of LiOH. The homogeneous solution was cast to form a thin and transparent SPE membrane. Characterization by X-Ray Diffraction (XRD) revealed the semi-crystalline properties of all samples. Ionic conductivity of SPEs composites was determined through AC impedance measurement using Electrochemical Impedance Spectroscopy (EIS). Among all samples that were studied, the sample with 4 wt. % LiOH revealed the highest ionic conductivity that reached 2.18 × 10-5 S.cm-1 at room temperature.