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Plug-in hybrid electric vehicles have the potential of combining the benefits of electric vehicle in terms of low emissions and internal combustion engine vehicles in terms of vehicle range. With the addition of a renewable fuel, the CO2 potential reduction increase even more. The last trends for PHEV are small combustion engine known as range extender, with battery package between full hybrid and electric powertrains. Thus, allowing an improvement in vehicle’s range, reducing battery materials while converting fuel energy through a highly efficient path. Although these vehicles have been proved to be a convenient strategy for decarbonizing the light vehicles, the use of alternative fuels is poorly studied. In this work, hydrous ethanol is chosen because is already available in some countries, such as USA and Brazil, and have an ultra-low well-to-tank CO2 emission.