Using the job demands-resources (JD-R) theory, this study aimed to understand how and when emotional leadership affected teachers' psychological well-being. It explored the mediating effect of emotional labour and the moderating effects of collectivism and two Confucian cultural values (i.e., harmony and obedience to authority). The sample included 2361 Chinese teachers from primary and secondary schools. Findings showed that emotional leadership as a job resource from leaders promoted deep acting (DA) and expression of naturally felt emotions (ENFE), eventually enhancing psychological well-being. Moreover, emotional leadership caused more surface acting (SA) only when teachers had a lower level of harmony, which reduced psychological well-being; collectivism, harmony, and obedience to authority weakened the positive impacts of emotional leadership on psychological well-being. This study contributes to the JD-R theory by revealing that leader factors could act as both resources and demands to influence personal factors under the moderating effect of cultural values.