Planning the best path for the energy system decarbonization is currently one of the issues of high global interest. At the European level, the recent policies dealing with the transportation sector have decided to ban the registration of light-duty vehicles powered by internal combustion engines fed by fossil fuels, from 2035. Regardless of the official positions, the major players (industries, politicians, economic and statistical institutions, etc.) manifest several opinions on this decision. In this paper, a mathematical model of a nation’s energy system is used to evaluate the economic impact of this decision. The model considers a superstructure that incorporates all energy conversion and storage units, including the entire transportation sector. A series of succeeding simulations was run and each of them was constrained to the achievement of the decarbonization level fixed, year by year, by the European community road-map. For each simulation, an optimization algorithm searches for a less costly global energy system, by including/excluding from the energy system the energy conversion units, storage devices, using a Mixed Integer Linear approach. Three optimization scenarios were considered: (1) a “free” scenario in which the only constraint applied to the model is the achievement of the scheduled decarbonization targets; (2) an “e-fuels” scenario, in which all new non-battery-electric light-duty vehicles allowed after 2035 must be fed with e-fuels; (3) a “pure electric” scenario, in which all new light-duty vehicles allowed after 2035 are battery-electric vehicles. The comparison of the optimum solutions for the three scenarios demonstrates that the less costly transition to a fully renewable energy system decarbonizes the transportation sector only when the share of renewable energy sources exceeds 90%. E-fueled light-duty vehicles always turn out to be a less expensive alternative than the electric vehicles, mainly because of the very high cost of the energy supply infrastructure needed to charge the batteries. Most of all, the costs imposed to society by the “e-fuels” and “pure electric” light-duty-vehicle decarbonizing scenarios exceed by 20% and 60%, respectively, the “free” transition scenario.