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. Lay description What is already known about this topic: Emotions and learner characteristics are assumed to influence multimedia learning. There are inconsistent results on emotional impact on multimedia learning. Cognitive resources were shown to be predictors of learning outcomes. There are inconsistent results on how much learners' personality predicts learning. What this paper adds: Negative emotions can lead to higher learning outcomes than positive emotions. Cognitive resources are significant predictors for learning outcomes. Openness to experience predicts learning outcomes. Neuroticism enhances the emotional impact on multimedia learning. Implications for practice and/or policy: Learner characteristics and emotions influence multimedia learning. A very positive emotional state can be harmful to learning. Learners' personality can enhance emotional impact on multimedia learning. Learning environments should be designed to attract learners' curiosity.