Highly motivated students often exhibit better academic performance than less motivated students. However, to date, the specific cognitive mechanisms through which motivation increases academic achievement are not well understood. Here we explored the possibility that mind wandering mediates the relation between motivation and academic performance, and additionally, we examined possible mediation by both intentional and unintentional forms of mind wandering. We found that participants reporting higher motivation to learn in a lecture-based setting tended to engage in less mind wandering, and that this decrease in mind wandering was in turn associated with greater retention of the lecture material. Critically, we also found that the influence of motivation on retention was mediated by both intentional and unintentional types of mind wandering. Not only do the present results advance our theoretical understanding of the mechanisms underlying the relation between motivation and academic achievement, they also provide insights into possible methods of intervention that may be useful in improving student retention in educational settings.