Salinity gradient power is a renewable, non-intermittent, and neutral carbon energy source. Reverse electrodialysis is one of the most efficient and mature techniques that can harvest this energy from natural estuaries produced by the mixture of seawater and river water. For this, the development of cheap and suitable ion-exchange membranes is crucial for a harvest profitability energy from salinity gradients. In this work, both anion-exchange membrane and cation-exchange membrane based on poly(epichlorohydrin) and polyvinyl chloride, respectively, were synthesized at a laboratory scale (255 cm2) by way of a solvent evaporation technique. Anion-exchange membrane was surface modified with poly(ethylenimine) and glutaraldehyde, while cellulose acetate was used for the cation exchange membrane structural modification. Modified cation-exchange membrane showed an increase in surface hydrophilicity, ion transportation and permselectivity. Structural modification on the cation-exchange membrane was evidenced by scanning electron microscopy. For the modified anion exchange membrane, a decrease in swelling degree and an increase in both the ion exchange capacity and the fixed charge density suggests an improved performance over the unmodified membrane. Finally, the results obtained in both modified membranes suggest that an enhanced performance in blue energy generation can be expected from these membranes using the reverse electrodialysis technique.