The need for sustainable transport is increasingly recognized and receives more and more attention. Cities face the challenge to enhance the quality of urban environment reducing traffic congestion, pollution and road accidents. Moreover, transport charging policies consist a basic tool for sustainable mobility while they are increasingly applied in urban centers. The objective of the present research is to investigate drivers’ acceptance of environmental transport charging policies with emphasis on environmental charging (annual card) for private cars access in Athens center. In order to achieve this objective, data were collected through a questionnaire survey, using stated preference methodology while a binary logistic regression model was developed to determine the acceptance of car access card in the center of Athens. The results demonstrate that annual card cost and travel time saving are the main factors for the acceptance of the annual card. Furthermore, men and young people are more likely to accept the annual card while several other parameters such as vehicle’s age and usage, vehicle’s engine capacity and driver’s perception of environmental pollutants affect policy’s acceptance and should be taken into account by policymakers when developing and implementing similar environmental mobility strategies.