Students entering post-secondary are subject to changes in their lifestyles, responsibilities, and expectations. For many students, these changes cause large amounts of stress, which may have an impact on their ability to be successful in post-secondary. Distinct from how students actually spend their time, how they believe they spend their time (i.e., time structure) may play an important role in the development of stress and thus impact their success in post-secondary. To date, the way post-secondary students perceive their time use is relatively unexplored, as its relationship to stress and academic success. The present study surveyed 319 first-year university students to determine if perceived stress acts as a mediator between time structure and academic success, and if the factors of time structure were related to perceived stress. The results show that perceived stress partially mediated the relationship. Time structure had a strong relationship with perceived stress. Time structure and perceived stress also had significant relationships with academic success. Correlations show that time structure factors relate to perceived stress, with sense of purpose and effective organization having the strongest relationships. Overall, the results suggested that promoting better time structure could be a valid intervention for improving perceived stress. Interventions that target other stress reducing factors, such as time management, could consider how time structure can contribute to stress in post-secondary students. Furthermore, counsellors who work with post-secondary students should consider the influence of time structure on the well-being of students.