This research assesses and analyzes the impacts on energy consumption and the related carbon dioxide (CO2) emissions resulting from the use of electric vehicles (EVs) when compared with internal combustion (IC) diesel vehicles fueled with biofuels. Enhancing commercial fossil diesel fuel with 15% biodiesel (B15) to be used by a fleet of light-duty diesel vehicles was considered the starting point for this study. Based on data collected from this IC vehicles fleet, it was possible to analyze and compare the energy consumption and the related emissions resulting from the use of EVs with the same work operation. This research showed that the use of EVs presents a few comparative advantages, but also has some significant limitations. On what concerns the global CO2 emissions and energy efficiency differences of both EVs and biodiesel fueled IC vehicles, these were not very significant. The use of electric motorization implies a 50% reduction in CO2 emissions compared with the reference fossil diesel fuel and the use of B15 and B30 correspond to a reduction of about 11.8% and 22.4%, respectively, in these same emissions. However, there are additional constraints related to economic factors since the purchase of EVs is significantly more expensive than that of similar IC vehicles. The use and fleet management of EVs is also more complex due to the limitation in terms of vehicle autonomy, requiring more EVs and more people for the same operation. Thus, this type of analysis shows to be essential to support selecting the most sustainable and efficient options for the operation of a light commercial vehicles fleet.