The environmental implications of converting vehicles powered by Internal Combustion Engines (ICE) to battery powered and hybrid battery/ICE powered are evaluated for the case of Chile, one of the worldwide leaders in the production of lithium (Li) required for manufacturing of Li-ion batteries. The economic and environmental metrics were evaluated by techno-economic analysis (TEA) and Life Cycle Assessment (LCA) tools - SuperPro Designer and Gabi®/GREET® models. The system boundary includes both the renewable and nonrenewable energy sources available in Chile and well-to-pump energy consumptions and GHG emissions due to Li mining and Li-ion battery manufacturing. All the major input data required for TEA and LCA were generated using Autonomie vehicle modeling software. This study compares economic and environmental indicators of three vehicle models for the case of Chile including compact, mid-size, and a light duty truck. Autonomie was utilized to predict the fuel economy for the hybrid electric vehicle (HEV) and electric vehicle (EV) for each of the three vehicle types. The baseline fuel economy without vehicle electrification for each case was 44, 29, and 19 mpg, respectively. The LCA and TEA results suggest that vehicle electrification for the case of Chile would improve the metrics of sustainability and economic impacts at the nationwide level. The electrification of compact, mid-size, and a light duty truck, reduce the nationwide GHG emissions by 27%, 47%, and 37%, respectively, for the HEV scenario. Use of renewable energies in vehicle electrification, including hydroelectric and photovoltaic energies, currently 39% of the generation mix, and gasoline usage reduction reduces GHG emissions of the country. The EV scenario; however, increases the GHG emissions of the subcompact vehicle by 22%, whereas this scenario reduces the emissions of the mid-size and the light-duty truck by 25% and 47%, respectively. Use of crude oil, natural gas, and coal in Chile, currently 61% of the generation mix, contributes to increase the life cycle emissions for the EV scenario. The results of this research demonstrate that vehicle electrification has a significant impact not only in the reduction of GHG emissions but also in the economy of the country. Overall, this research will help policymakers and scientific communities to develop strategies to promote and research HEV and EV.