Poly(vinyl chloride) (PVC) based electrolytes, a class of the most promising polymer electrolytes, are found to suffer from solvent exudation. Two strategies were employed to suppress this shortcoming, one involving the replacement of PVC with poly(vinyl chloride-co-vinyl acetate) (PVCAC) copolymer and the other the direct utilization of solvents for PVC or PVCAC instead of using an auxiliary carrier solvent (e.g., tetrahydrofuran, THF). The thermodynamics of polymer solubility was particularly emphasized in the latter approach. N,N-dimethylformamide (DMF) and N-methyl pyrrolidionone (NMP) are preferred cosolvents of ethylene carbonate (EC) and/or propylene carbonate (PC). The PVCAC-based gel electrolytes prepared were then characterized by ionic conductivity, cyclic voltammetry, and ac impedance data. The results indicate that electrolytes containing NMP/EC mixed solvent exhibit conductivities exceeding 10(-3) S cm(-1) whereas the electrolytes containing DMF/EC/PC exhibit conductivities around 10(-4) S cm(-1) at room temperature. Moreover, the former category was found to be oxidatively stable up to 4.9 V vs. Li/Li+ and the latter to 4.6 V vs. Li/Li+. Finally, ac impedance results suggest that the stability.