Flow is an optimal experience resulting in intense engagement in the activity. People achieved flow state when they perceived balance between challenge of the activity and their skill to the activity. The concept of flow can be used to explore students’ learning performance in e-learning environment. The current research aims to empirically explore the influence of challenge-skill balance on the flow experience and the influence of flow experience on learning satisfaction and learning performance in e-learning environment. The current research conducted a quasi-experimental design with questionnaire survey and carried out an electroencephalography (EEG) analysis, a psychophysiological method. The empirical survey results have shown that challenge-skill balance is an antecedent factor affecting learners’ flow experience. Once learners reach flow experience, their learning performance and learning satisfaction would get improved. Besides, the current research also found that flow experience is relative with learners’ attention measured by EEG brainwave signal. Learners’ perception of challenge-skill balance would influence their attention in e- learning activities. The current research is also in the pioneering position that using non-medical purpose EEG device in e-learning research.