In this present paper the influence of viscosity on the ionic dynamics of polymer gel electrolytes prepared by the Pechini polymeric precursor method is investigated by impedance spectroscopy, differential scanning calorimetric (DSC) and NMR techniques. Polymer gel electrolytes are formed by ethylene glycol (EG) and citric acid (CA) and lithium perchlorate. Room temperature conductivity of the order of 2.3×10−4 S/cm was obtained for the sample of EG/CA:LiClO4 with lower viscosity (η =197cP). The results show that the ionic conductivity of the electrolytes increases for decreasing viscosity. Proton (1H) and Lithium (7Li) NMR lineshapes and spin–lattice relaxation times were measured as a function of temperature and viscosity (197–868cP). The 7Li relaxation process was found to be dominated by quadrupolar couplings. The activation energy extracted from the 1H and 7Li relaxation data (∼0.23eV) was found to be independent of the viscosity of the gel electrolyte. The 7Li NMR relaxation results indicate an increase of the lithium ion mobility with decreasing viscosity.