The growth in the number of vehicles circulating has led to a proportional increase in polluting gas emissions. Bioenergy can be used to help meet these increasing energy demands and mitigate environmental impacts. This work verified the effect of the content of ethanol on the exergy and exergoenvironmental analyses of a spark-ignition engine. Different gasoline−ethanol mixtures were tested along with hydrous ethanol (4.6% water by volume). The thermodynamic data refer to wide-open throttle conditions and variable engine speeds. The life cycle assessment methodology quantified the environmental impacts associated with equipment and fuel using the Eco-indicator 99 method. Pollutants emitted during combustion were measured and included in the environmental assessment (nitrogen oxides, carbon monoxide, and dioxide). Hydrous ethanol at 1500 rpm presented the highest energy efficiency. The effects of the environmental impact rate of pollutant formation and exergy efficiency were significantly higher than the environmental impact rate of fuel. The lowest specific environmental impact of the product (brake power) was 24.39 mPt/MJ, obtained with the fuel blend with 50% ethanol at 2500 rpm. The combined evaluation of the exergoenvironmental factor and the relative difference in environmental impact indicated the optimization priorities and where improvements should be directed.