Previous studies found that teachers’ psychological capital positively affects their workplace well-being. However, the underlying internal mechanism behind this relationship remains ambiguous. The current study aimed to investigate the effects of ego-resiliency and work-meaning cognition on this relationship among Chinese teachers. The questionnaire, including the psychology capital scale (PCS), workplace well-being subscale (WWBS), Psychological Empowerment Scale (PESS), and Ego-Resiliency Scale (ERS), was used to collect data points from 1388 primary and secondary school teachers. The results reveal that: (1) teachers’ psychological capital positively predicts workplace well-being; (2) work-meaning cognition mediates the relationship between teachers’ psychological capital and workplace well-being; (3) the influence of work-meaning cognition on the relationship between teachers’ psychological capital and workplace well-being is moderated by ego-resiliency. These findings explore the factors that affect well-being and point to potential ways to enhance teachers’ workplace well-being.