According to self-determination theory, an individual’s goal content and the processes involved in goal setting often represent the status of the individual’s mental health and well-being. When examining the importance placed on goal setting, an individual’s goals and aspirations are often synonymous with mental health and well-being. Aspiring to achieve intrinsic life goals has been associated with greater psychological well-being in literature. This study therefore aimed to establish the relationships between goals and aspirations, mental health behaviour (interpersonal relations, stress management, and spiritual growth), and psychological well-being (measured by positive affect). A sample of 457 secondary school learners in the Overberg Educational District, Western Cape, South Africa, participated in the study. The results suggest a significant positive relationship between placing importance on intrinsic goals and aspirations, and psychological well-being (as indicated by positive affect). However, psychological well-being was not correlated with mental health behaviour. The results of the hierarchical regression analysis suggest that importance placed on intrinsic goals and aspirations predicts psychological well-being and accounts for 8% of the variance. The results highlight the role of intrinsic goals and aspirations in predicting the psychological well-being of adolescents. The findings are supported by the theoretical assumptions of self-determination theory.