Facilitating coordination between economic growth and carbon mitigation is vital for the sustainability of human society. Identifying the driving factors of Carbon emission performance (CEP) is crucial for its improvement. Nevertheless, empirical research on the relationship between advanced human capital structure (AHCS) and CEP remains scarce. This study analyzes the impact of AHCS on CEP utilizing a dataset covering 30 Chinese provinces from 2006 to 2021. First, we construct a global epsilon-based measure (EBM) model with undesired output to accurately measure the multi-period CEP for Chinese provinces. Next, we evaluate the level of AHCS from the perspective of dynamic evolution. Subsequently, a spatial Durbin model (SDM) is employed to examine the spatial spillover effects of AHCS on CEP. The results illustrate that CEP exhibits significant positive spatial spillover effects across provinces. Additionally, AHCS has a direct and significant positive impact on local CEP and can indirectly enhance CEP in neighboring regions through spillover effects, although the impact varies across different regions. The impact mechanism analysis indicates that AHCS enhances CEP via technological advancement, industrial structure upgrading (ISU), and energy efficiency improvement, despite the asymmetric effects observed between local and neighboring provinces. Therefore, shaping a favorable educational environment to optimize the human capital structure is critical for the improvement of CEP. In addition, promoting resource sharing and technology exchange through regional cooperation is essential for China’s low-carbon transition development.