Although intelligent tutoring systems (ITSs) are increasingly used, it is unclear which psychological processes precede students' learning gains. Using a pre- and posttest design, the present study examined a sequence of psychological processes informed by control value theory. We investigated (a) whether secondary school students' topic-related cognitive appraisals (value and control) affected their task-related affective (enjoyment and boredom) and cognitive (engagement and performance) outcomes while using the ITS and (b) whether task-related outcomes affected learning. Path analyses showed that students’ topic-related interest, but not perceived utility, personal importance or self-efficacy, was associated with task-related enjoyment. In turn, enjoyment showed reciprocal effects on and of engagement and ongoing task performance, which predicted final performance and, ultimately, learning gains. The influence of boredom, in contrast, was minimal along this sequence. More generally, the findings highlight the difficulty of establishing a clear pattern of sequential causation derived from control value theory for the current ITS context, with evidence demonstrating the systematic influence of confounders accounting for the predicted relations among components. Despite these limitations, we identified key psychological processes involving the contribution of affective and cognitive processes to learning in the ITS context.