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In the present work, a novel polymer composite electrolytes (PCEs) based on poly(vinyl alcohol) (PVA) ammonium thiocyanate (NH4SCN) Cd(II)-complex plasticized with glycerol (Gly) are prepared by solution cast technique. The film structure was examined by XRD and FTIR routes. The utmost ambient temperature DC ionic conductivity (σDC) of 2.01 × 10-3 S cm-1 is achieved. The film morphology was studied by field emission scanning electron microscopy (FESEM). The trend of σDC is further confirmed with investigation of dielectric properties. Transference n