Various aspects of intrinsic motivation have long been theorized as key determinants of learning achievement. The present research seeks deeper insights into these intrinsically motivating mechanisms by investigating neurophysiological correlates of cognitive absorption in the context of enactive learning, specifically simulation-based training on the use of enterprise resource planning (ERP) software. An experiment was conducted in which 36 student trainees used ERP software to make decisions while running a simulated company. Consistent with flow theory, skill, difficulty, and their interaction significantly influenced cognitive absorption (R2 = .16). Five neurophysiological measures were captured for each trainee: EEG alpha, EEG beta, electrodermal activity (EDA), heart rate, and heart rate variability. Each of the five neurophysiological measures explained significant unique variance in cognitive absorption over and above skill, difficulty, and their interaction, and collectively more than doubled the explained variance to R2 = .34. Overall, cognitive absorption was positively related to a more relaxed, less vigilant state. Cognitive absorption was significantly related to the training outcome. These findings provide new insights into the psychological states that are conducive to experiencing cognitive absorption during enactive training.