The aim of this research is an evaluation of polyelectrolytes. In the application of zinc-iodine batteries (ZIBs), polyelectrolytes have high stability, good cationic exchange properties and high ionic conductivity. Polyelectrolytes are also cost-effective. Important component of ZIBs are cation exchange membranes (CEMs). CEMs prevent the crossover of iodine and polyiodide from zinc (Zn) electrodes. However, available CEMs are costly and have limited ionic conductivity at room temperature. CEMs are low-cost, have high stability and good cationic exchange properties. Herein, polyelectrolyte membranes prepared from carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) are examined. It is seen that an increase in the ratio of PVA leads to enhanced ionic conductivity as well as increased iodine and polyiodide crossover. ZIBs using polyelectrolytes having 75:25 wt.% CMC/PVA and 50:50 wt.% CMC/PVA show decent performance and cycling stability. Due to their low-cost and other salient features, CMC/PVA polyelectrolytes prove they have the capacity for use as cation exchange separators in ZIBs.