Application of multimedia learning in physical education is very common. However, simply playing video clips does not provide any opportunity for interaction with users, leading to low learning motivation and poor learning outcomes in students. In this study, the ARCS theory of motivation is incorporated, and a set of 3D multimedia volleyball learning materials on serving, setting, catching, and blocking have been designed. Motion capture equipment was used to record players' actual moves, so as to ensure authenticity of the actions in the learning materials. An APP is used to present the content of the learning materials via a tablet. By swiping the tablet with their fingers, users can adjust the viewing angles of the videos, and the playback speed can be adjusted via buttons. These two functions increase the interactivity of the learning materials. In addition, learning motivation is enhanced through detailed explanations in text boxes and voice prompts for each step of the actions. For the experiment, 173 undergraduate students in the Kaohsiung campus of Shih Chien University were tested for their learning motivation and self-learning outcome after using the multimedia learning materials. The results show that the students' scores in all factors of the ARCS motivational model (Attention, Relevance, Confidence, and Satisfaction) are above average, and "Association" has the highest mean score out of all factors. Furthermore, in both learning motivation and self-learning outcome, male students scored significantly higher than female students, students in the College of Business and Information scored significantly higher than those in the College of Culture and Creativity, and users who had experience with multimedia learning materials scored significantly higher than those with no experience. The contribution of this study is that it developed learning materials based on the ARCS theory of motivation from the perspective of multimedia design, and the materials are proven to be able to effectively enhance learning motivation and boost self-learning outcome.