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With gradual adoption of “multimedia” technologies on the curriculum designs in modern education, there are increasing needs for in-depth studies thoroughly exploring how different types of multimedia materials affecting learner's emotion and their learning performance. By the introduction of technological advancement on human physiological signals recognizing emotional variances, reliable emotion monitoring application is developed for measuring and recording human emotion changes in practical uses. This study adopted emotion detector system, emWave, measuring changes of learners' emotional state correspond to different types of multimedia materials. By analyzing the collected data and assessment on learning performance, this study attempts to explore how different types of multimedia materials affecting learners' learning emotion; ultimately, their learning performance. The result shows that different types of multimedia materials will significantly affect their learning performance and learning emotion; however, there is low correlation between learning emotion and learning performance.