Fostering and sustaining affective commitment of teachers has been an everlasting topic given its significance in enhancing performance of both teachers and schools. However, it is still unclear whether high performance work systems (HPWS) can enhance teachers' affective commitment and work sense of gain (WSG), particularly with respect to individual differences such as career goals. Following the Job-Demand Resources (JD-R) Theory, this study employed a random sampling method and collected data from 922 Chinese teachers across different schools. After constructing a structural model with Mplus 8.3, this study revealed the mediating role of WSG between HPWS and affective commitment of teachers, alongside the moderating role of career goals in enhancing WSG, especially material rewards. Findings of this research not only enriched the application of JD-R Theory in the teacher education field but also highlighted the importance of HPWS in predicting better affective commitment and WSG of teachers from the perspective of school management. More importantly, educational administrators can take the reference to HPWS with an aim to facilitate career goals and WSG of teachers, thereby strengthening teachers' affective commitment and work performance across schools.