Objectives: Teachers’ intention understanding ability reflects their professional insight, which is the basis for effective classroom teaching activities. However, the cognitive process and brain mechanism of how teachers understand students’ action intention in class are still unclear. Methods: This study used event-related potential (ERP) technology to explore the cognitive neural differences in intention understanding ability among teachers with different levels of knowledge and experience. The experiment used the comic strips paradigm to examine the ability of expert and novice teachers to understand students’ normative and non-normative classroom actions under different text prompts (“how” and “why”). Results: The results revealed that in the late time window, expert teachers induced larger P300 and LPC amplitudes when they understood students’ classroom action intentions, while the N250 amplitudes induced by novice teachers in the early time window were significantly larger. In addition, for both types of teachers, when understanding the intentions behind students’ normative actions, the N250 amplitude was the most significant, while the P300 and LPC amplitudes were more significant for non-normative actions. Conclusions: This study found that teachers at varying professional development stages had different time processing processes in intention understanding ability, which supported teachers’ brain electrophysiological activities related to social ability.