<p>Education for Sustainable Development (ESD) has emerged as a priority for higher education institutions seeking to equip learners with the competencies required to address complex global challenges. Despite its importance, empirical evidence on critical thinking abilities and ESD behaviours among higher education students in developing contexts remains limited. Therefore, the study explored how critical thinking competencies influenced sustainability-related attitudes and actions in higher education settings. A cross-sectional survey design was employed, with a sample of 549 students selected via simple random sampling from three Technical Universities in Ghana. Data were collected using the Gardiner Critical Thinking Scale to measure CT abilities and the newly developed Education for Sustainable Development Scale (ESDS-20) to assess ESD behaviours. Descriptive statistics were used to assess the levels of CT and ESD behaviours, while covariance-based structural equation modelling (CB-SEM) was applied to evaluate the predictive relationships between various CT dimensions and ESD behaviours. The results revealed that students exhibited significantly high levels of both CT abilities and ESD behaviours. Additionally, the study showed that specific CT components, including creative character, resistance to premature closure, and synthesising abilities, significantly predicted key ESD behaviours, such as systems thinking, sustainable action, and ethical responsibility. This study contributes to the growing body of knowledge by demonstrating that CT competencies play a vital role in shaping students’ engagement with sustainability issues. The findings underscore the importance of integrating critical thinking pedagogies, interdisciplinary sustainability curricula, and experiential learning opportunities in higher education to enable students to apply reflective reasoning to real-world sustainability challenges.</p>