The present research examined the connections between temperament (punishment sensitivity; interindividual reward sensitivity; intraindividual reward sensitivity), students’ domain- and course-specific motivational appraisals (interest, strain, effort), and performance, in two studies. Study 1 explored the relationships between temperamental sensitivities, motivational appraisals, and task achievement among secondary students (N = 268) in the domain of mathematics, using Exploratory Structural Equation Modeling (ESEM) for the analyses. Study 2 was conducted longitudinally among upper-secondary students (N = 155) during a course in four key school subjects. Subject interest was included alongside the temperamental sensitivities as a predictor of course-specific motivation and course grades, and the data were analysed with Partial Least Squares Structural Equation Modeling (PLS-SEM). Previous achievement was controlled in both studies. The findings showed temperamental sensitivities to be differentially linked with motivational appraisals. Punishment sensitivity in Study 1, and interindividual reward sensitivity (sensitivity to reward dependent on others’ approval or attention) in Study 2 were found to have an effect on psychological strain. In both studies, interest and effort were predicted by intraindividual reward sensitivity (positive responsiveness to novelty and own successes). In Study 2, subject interest was a consistent predictor of higher course interest and lower strain. In both studies, connections were found between strain and lower performance. The findings suggest individual characteristics may predispose students to certain motivational experiences, and contribute to educational outcomes, in both domain and course contexts and across subject content.