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Summary: The quantity of electric vehicles in the transport sector has steadily risen over the last 10 years. Most developed countries and China have laid out ambitious plans for electric vehicles penetration. However, there are several challenges that must be addressed on the supply‐chain side of the problem for a successful transition toward an alternative and less environmentally harmful transport system. This study proposes a methodology for the optimal plan and decision making of primary energy sources, electricity generation, electricity distribution to vehicles' charging stations, carbon capture and sequestration, and electric vehicles' charging stations network to satisfy the electricity demand of the overall economy including electric vehicles at a regional/countrywide level under operation and green constraints. The optimization problem was modeled as a mixed integer program in general algebraic modeling system (GAMS). The formulation was employed to propose the upcoming electricity supply chain for electric vehicles in the most populous German state (North Rhine‐Westphalia) in 2025. The optimization show that fossil‐based power still controls the generation in 2025, while carbon capture and sequestration along with higher renewable penetration help meeting the state's greenhouse gases (GHG) emission target. The charging stations network expansion consists of 12 820 charging points mainly alternating current (AC) chargers (22‐kW capacity). [ABSTRACT FROM AUTHOR]