An attempt has been made in the present work to cast stable polymeric gel electrolytes by drying as-synthesized gel electrolytes which were prepared by sol gel process. The polyvinyl alcohol (PVA) has been used as matrix in the gel to hold ammonium thiocyanate (NH4SCN) dissolved in dimethyl sulfoxide (DMSO). DSC studies reveal the presence of pristine materials along with PVA-NH4SCN complexes. The FTIR spectral studies affirm complex formation. Ionic conductivity of gel electrolytes shows maxima at 6 wt.% of PVA. The conductivity response has been correlated to complexation behaviour. Temperature dependence of ionic conductivity revealed the existence of liquid like conduction at lower wt.% of incorporated PVA whereas contribution to conductivity by polymeric complexes enhanced at higher wt.% of polymer. (C) 2007 Elsevier B.V. All rights reserved.