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There is a strong increase in the use of devices that measure physiological arousal through electrodermal activity (EDA). Although there is a long tradition of studying emotions during learning, researchers have only recently started to use EDA to measure emotions in the context of education and learning. This systematic review aimed to provide insight into how EDA is currently used in these settings. The review aimed to investigate the methodological aspects of EDA measures in educational research and synthesize existing empirical evidence on the relation of physiological arousal, as measured by EDA, with learning outcomes and learning processes. The methodological results pointed to considerable variation in the usage of EDA in educational research and indicated that few implicit standards exist. Results regarding learning revealed inconsistent associations between physiological arousal and learning outcomes, which seem mainly due to underlying methodological differences. Furthermore, EDA frequently fluctuated during different stages of the learning process. Compared to this unimodal approach, multimodal designs provide the potential to better understand these fluctuations at critical moments. Overall, this review signals a clear need for explicit guidelines and standards for EDA processing in educational research in order to build a more profound understanding of the role of physiological arousal during learning.