Shaping a secure and sustainable energy future may require a set of transformations in the global energy sector. Although several studies have recognized the importance of Electric Vehicles (EVs) for power systems, no large-scale studies have been performed to assess the impact of this technology in energy systems combining a diverse set of renewable energies for electricity production and biofuels in the transportation sector such as the case of Brazil. This research makes several noteworthy contributions to the current literature, including not only the evaluation of the main impacts of EVs’ penetration in a renewable electricity system but also a Life-Cycle Assessment (LCA) that estimates the overall level of CO2 emissions resulted from the EVs integration. Findings of this study indicated a clear positive effect of increasing the share of EVs on reducing the overall level of CO2 emissions. This is, however, highly dependent on the share of Renewable Energy Sources (RES) in the power system and the use of biofuels in the transport sector but also on the credits resulting from the battery recycling materials credit and battery reuse credit. Our conclusions underline the importance of such studies in providing support for the governmental discussions regarding potential synergies in the use of bioresources between transport and electricity sectors.