Unlike the other studies on emotional design in multimedia learning, the present study differentiated the two confounding variables of visual interface design and structured content to manipulate the instructional material. Specifically, we investigated how the visual aesthetics of positive emotional interface design influenced learners' cognitive processes, emotional valences, learning outcomes, and subjective experience. Eighty-one college students took part in the experimental study. They were divided into the three experimental groups: a holistic layout of positive emotional design group (HPED), a local layout of positive emotional design group (LPED), and a neutral emotional design group (ND). By using a mixed approach of questionnaires and eye tracking, we further explored the differences among the three groups in cognitive processing, learning outcomes, and subjective experience. Results indicated that the LPED group invested higher cognitive effort, put more attentional focus in the relevant knowledge content module, and achieved better learning performance (i.e., retention and transfer tests) in contrast to the HPED group and the ND group. However, no significant difference in dynamic changes of emotional state among the three groups was detected. The analytical results can provide researchers and practitioners with valuable insights into the positive emotional design of multimedia learning, which allows for the facilitation of mental engagement, learning outcomes and subjective perception.