An attempt has been made in the present work to combine gel and composite polymer electrolyte routes together to form a composite polymeric gel electrolyte that is expected to possess high ionic conductivity with good mechanical integrity. Polyethylene glycol (PEG) based composite gel electrolytes using polyvinyl alcohol (PVA) as guest polymer have been synthesized with 1 molar solution of ammonium thiocyanate (NH₄SCN) in dimethyl sulphoxide (DMSO) and electrically characterized. The ionic conductivity measurements indicate that PEG : PVA : NH₄SCN-based composite gel electrolytes are superior ($\sigma_{\text{max}} = 5.7 \times 10^{−2}$ S cm^-1) to pristine electrolytes (PEG : NH₄SCN system) and conductivity variation with filler concentration remains within an order of magnitude. The observed conductivity maxima have been correlated to PEG : PVA : NH₄SCN- and PVA : NH₄SCN-type complexes. Temperature dependence of conductivity profiles exhibits Arrhenius behaviour in low temperature regime followed by VTF character at higher temperature.