In this work, we report the preparation of Nafion membranes containing two different nanocomposite MF-4SC membranes, modified with polyaniline (PANI) by the casting method through two different polyaniline infiltration procedures. These membranes were evaluated as a polymer electrolyte membrane for water electrolysis. Operating conditions were optimized in terms of current density, stability, and methanol concentration. A study was made on the effects on the cell performance of various parameters, such as methanol concentration, water, and cell voltage. The energy required for pure water electrolysis was analyzed at different temperatures for the different membranes. Our experiments showed that PEM electrolyzers provide hydrogen production of 30 mL/min, working at 160 mA/cm2. Our composite PANI membranes showed an improved behavior over pristine perfluorinated sulfocationic membranes (around 20% reduction in specific energy). Methanol-water electrolysis required considerably less (around 65%) electrical power than water electrolysis. The results provided the main characteristics of aqueous methanol electrolysis, in which the power consumption is 2.34 kW h/kg of hydrogen at current densities higher than 0.5 A/cm2. This value is ~20-fold times lower than the electrical energy required to produce 1 kg of hydrogen by water electrolysis.