A new approach for the simultaneous generation of electric energy and the treatment of waters contaminated by recalcitrant pollutants using salinity gradients was proposed. Reverse electrodialysis allows for the generation of electric energy from salinity gradients. Indeed, the utilization of different salt concentrations gives a potential difference between the electrodes which allows the generation of electric energy by using suitable electrolytes and an external circuit. The simultaneous generation of electric energy and the treatment of waters contaminated by Cr(VI) was successfully achieved for the first time by reverse electrodialysis processes using salinity gradients and proper redox processes. The effect on the process of many operative parameters, such as the extent of the salinity gradient, the number of membrane pairs in the stack, the initial concentration of Cr(VI), the concentration of the supporting electrolyte and the flow rates of the solutions fed in the stack, was also investigated.