An electrodialysis (ED) process was tested for volatile fatty acids (VFA) recovery from a simulated leachate of acidogenesis of municipal solid wastes (MSW). The effect of initial VFA concentration in leachate, applied voltage and flow rate on VFA removal efficiency were evaluated. Four different leachate compositions were examined at three different applied voltages and at three different flow rates. Higher removal levels were obtained at low VFA initial concentration, high voltages levels and high flow rates. ED process was showed higher removal efficiency with shorts chain acids, but VFA final concentration was directly related with initial concentration of each acid. After VFA recovery tests of chemical reaction with ethanol were carried out for ethyl esters production as gas oil additives. Results of these tests showed a transformation efficiency of 26%.