Polymer electrolytes consisting of polyvinyl chloride (PVC) and poly (butyl methacrylate) (PBMA) as polymers, lithium hexafluorophosphate (LiPF6) as complex salt and 1-butyl 3-methylimidazolium hexafluorophosphate (BmImPF6) as plasticizer were prepared by solution casting technique. The effect of ionic liquid (BmImPF6) on PVC-PBMA blend polymer electrolytes are investigated by AC impedance, dielectric and SEM analysis to elucidate their electrical, dielectric and surface morphological assessment. Ionic conductivity of the prepared polymer electrolytes is found to be in the order of 10-3 S cm-1. Polymer electrolyte with PVC-PBMA-LiPF6-BmImPF6 (17-17-06-60) is found to be a potential candidate in battery applications.