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This paper focuses on the interdependent relationship of power generation, transportation and CO2 emissions to evaluate the impact of electric vehicle deployment on power generation and CO2 emissions. The value of this evaluation is in the employment of a large-scale, bottom-up, national energy modeling system that encompasses the complex relationships of producing, transforming, transmitting and supplying energy to meet the useful demand characteristics with great technological detail. One of such models employed in this analysis is the BUEMS model. The BUEMS model provides evidence of win-win policy options that lead to profitable decarbonization using Turkey’s data in BUEMS. Specifically, the result shows that a ban on diesel fueled vehicles reduces lifetime emissions as well as lifetime costs. Furthermore, model results highlight the cost-effective emission reduction potential of e-buses in urban transportation. More insights from the results indicate that the marginal cost of emission reduction through e-bus transportation is much lower than that through other policy measures such as carbon taxation in transport. This paper highlights the crucial role the electricity sector plays in the sustainability of e-mobility and the value of related policy prescriptions.