The CO2 reduction promise must be widely adopted if governments are to decrease future emissions and alter the trajectory of urban mobility. However, from a long-term perspective, the strategic vision of CO2 mitigation is driven by inherent uncertainty and unanticipated volatility. As these issues emerge, they have a considerable impact on the future trends produced by a number of exogenous and endogenous factors, including Political, Economic, Social, Technological, Environmental, and Legal aspects (PESTEL). This study’s goal is to identify, categorize, and analyze major PESTEL factors that have an impact on the dynamics of urban mobility in a rapidly changing environment. For the example scenario of the city of Larissa, Greece, a Fuzzy Cognitive Map (FCM) approach was employed to examine the dynamic interactions and behaviors of the connected criteria from the previous PESTEL categories. An integrative strategy that evaluates the interaction of linguistic evaluations in the FCM is used to include all stakeholders in the creation of a Decision Support System (DSS). The methodology eliminates the uncertainty brought on by a dearth of quantitative data. The scenarios in the study strands highlight how urbanization’s effects on sustainable urban transportation and the emergence of urban PESTEL actors impact on CO2 reduction decision-making. We focus on the use case of Larissa, Greece (the city of the CIVITAS program), which began putting its sustainable urban development plan into practice in 2015. The proposed decision-making tool uses analytics and optimization algorithms to point responsible authorities and decision-makers in the direction of Larissa’s sustainable urban mobility and eventually the decarbonization of the urban and suburban regions.