The Cognitive-Affective Theory of Learning with Media postulates that affective factors as well as individual learner characteristics impact multimedia learning. The present study investigated how experimentally induced positive and negative emotions influence multimedia learning and how learner characteristics moderated this impact. Results showed that the group with the negative emotion induction outperformed the group with the positive emotion induction with regard to learning outcome. Cognitive resources (working memory capacity, prior knowledge) and openness to experience were significant predictors for learning. In addition, learners with highest prior knowledge or working memory capacity could compensate the emotional impact on learning. Neuroticism enhanced the emotional impact on learning outcome as a moderator.