Enhancing the occupational well-being of early childhood teachers is of vital importance for the stability of the teaching workforce and the improvement of educational quality, as well as the healthy development of young children. This study surveyed 327 early childhood teachers using the Principal Transformational Leadership Scale, the Early Childhood Teacher Occupational Well-being Scale, the Psychological Empowerment Scale, and the Perceived Social Support Scale. The results are as follows: (1) Transformational leadership has a positive influence on the occupational well-being of early childhood teachers, and psychological empowerment mediates the relationship between transformational leadership and occupational well-being. (2) Perceived social support among early childhood teachers moderates the relationship between psychological empowerment and occupational well-being. Specifically, when teachers have a lower level of perceived social support, the predictive role of psychological empowerment on occupational well-being is stronger. Conversely, when teachers have a higher level of perceived social support, the predictive role of psychological empowerment on occupational well-being is not significant.