In the current context, where environmental concerns are gaining increased attention, the transition toward sustainable urban mobility stands out as a necessary and responsible step. Technological advancements over the past decade have brought private autonomous vehicles, particularly those defined by the Society of Automotive Engineers Levels 4 and 5, into focus as promising solutions for mitigating road congestion and reducing greenhouse gas emissions. However, the extent to which Autonomous Vehicles can fulfill this potential depends largely on user acceptance, patterns of use, and their integration within broader green energy and sustainability policies. The present paper aims to develop an integrated conceptual model that links behavioral determinants to environmental outcomes, assessing how individuals’ intention to adopt private autonomous vehicles can contribute to sustainable urban mobility. The model integrates five psychosocial determinants—perceived usefulness, trust in technology, social influence, environmental concern, and perceived behavioral control—with contextual variables such as energy source, infrastructure availability, and public policy. These components interact to predict users’ intention to adopt AVs and their perceived contribution to urban sustainability. Methodologically, the study builds on a narrative synthesis of the literature and proposes a framework applicable to empirical validation through structural equation modeling (SEM). The model draws on established frameworks such as Technology Acceptance Model (TAM), Theory of Planned Behavior, and Unified Theory of Acceptance and Use of Technology, incorporating constructs including perceived usefulness, trust in technology, social influence, environmental concern, and perceived behavioral control, constructs later to be examined in relation to key contextual variables, including the energy source powering Autonomous Vehicles—such as electricity from mixed or renewable grids, hydrogen, or hybrid systems—and the broader policy environment (regulatory frameworks, infrastructure investment, fiscal incentives, and alignment with climate and mobility strategies and others). The research provides relevant directions for public policy and behavioral interventions in support of the development of clean and smart urban transport in the age of automation.