With the gradual adoption of multimedia technologies in curriculum designs, the need has increased for in-depth studies exploring how different presentation techniques for multimedia materials affect learner emotions and learner performance. Therefore, this study employed the emWave system, which is a stress detector for emotional states developed by the Institute of HeartMath for measuring changes in learner emotional states when presented with different multimedia materials with same learning content. By analyzing the collected emotional data and assessment of learning performance, this study explores how different multimedia learning materials affect learning emotions, and ultimately, learning performance. Experimental results show that the video-based multimedia material generates the best learning performance and most positive emotion among three types of multimedia materials assessed in the study. Moreover, a partial correlation exists between negative learning emotion and learning performance.