This study examines sustainable mobility intention in a university population, based on an online survey of 2,192 respondents (1,499 students and 693 staff). Drawing on the Rubicon Model of Action Phases and the Action-Phase Model of Developmental Regulation, we applied Partial Least Squares Structural Equation Modeling (PLS-SEM) to examine how sustainable mobility intention is associated with the cognitive salience of perceived barriers and transport modality during the pre-actional phase. Results show that stronger sustainable commuting intentions are associated with greater cognitive salience of specific barriers, particularly those related to commute time, cost, distance, and infrastructure limitations—indicating intensified appraisal during the pre-actional phase. The association between intention and transport modality was limited to students. These findings suggest that interventions targeting the pre-actional phase should focus on awareness, informational support, and reducing perceived constraints, while acknowledging that different barriers may trigger primary or secondary control strategies in goal pursuit.