The objective of this paper is the appraise of the socioeconomic impacts until 2035 of a proposed annual charging policy called Green Car Access Card (GCAC) for the daily access of a passenger car in the city center of Athens, Greece with the charging being adjusted according to the Euro class. A questionnaire survey was conducted, using stated preference while a binary logistic model was developed to determine the acceptability of GCAC. A socioeconomic analysis is developed to quantify the impact on traffic, road safety, air pollution and climate change until 2035 due to the implementation of the policy. Specifically, for the “Do Nothing” Scenario and the “GCAC” Scenario the casualties on road accidents, the travel time, the fuel consumption and the emissions from motorized transport are estimated and expressed in monetary units. Results indicate a high and positive Net Present Value which proves that the proposed investment provides a significant benefit to society and commuters.