An important aspect of post-secondary student travel behaviour is their commute mode usage frequencies. How frequently students use different transportation modes for their daily travel directly characterizes their habits, routines, and predispositions, which can ultimately affect long-term social welfare of the region, congestion of the transportation network, and fuel consumption. Thus, obtaining an in-depth and unbiased understanding of the various factors influencing this travel behavior is key to the sustainable transportation development of a region. Existing studies on this topic are not comprehensive enough in terms of the types of commute modes analyzed and most of them relied on relatively small samples for their investigation. This paper attempts to address the gap by modelling the influence of personal and household socio-demographic attributes, the built environment, commute characteristics, and personal attitudes of the students on the monthly usage frequency of five different types of commute modes (auto, transit, ride-hailing, bicycle, and walk). It uses data from a large-scale student travel survey conducted among 10 post-secondary institutions in the Greater Toronto and Hamilton Area. The study makes use of a sophisticated modelling approach, consisting of a multiple indicators multiple causes model and a zero-inflated ordered probit model to analyze the factors affecting the decision to use and the usage frequency of the exhaustive set of commute modes. The findings emphasize the importance of commute distance, available resources (in terms of mobility tools, living situation, household vehicles, and income), and built environment attributes in the usage frequency of different commute modes. Marginal effects are used to inform actionable policy recommendations for both the institutions and the regional municipalities. The recommendations include offering discounted and promotional transit passes to encourage students to use public transit frequently, increasing the capacity of student housing and enhancing the sidewalk and bicycle infrastructure within 3–5 km of the campus locations, and increasing the transit accessibility of the institutions by establishing subway stops in proximity to the campuses. These recommendations, when implemented, will help to adequately meet the travel needs of the students while also improving their overall campus life experience.