The thermal power industry is a major anthropogenic source of emissions in China, significantly contributing to the release of carbon dioxide (CO2) and air pollutants. This study evaluated emission reduction potential under various scenarios by establishing the latest, real-monitored, and unit-level emissions database of particulate matter (PM), sulfur dioxide (SO2), nitrogen oxide (NOx), and CO2 for Chinese thermal power industry during 2021-2023. The results indicate that, during 2022-2023, the concentrations of PM, SO2, NOx, and CO2 decreased by 1.40 %, 0.83 %, 0.94 %, and 36.93 %, respectively. However, these reductions were insufficient to offset the impact of increased fuel consumption, leading to a rise in emissions of PM, SO2, NOx, and CO2 by 21.42 %, 13.43 %, 17.49 %, and 5.28 %, respectively. In 2023, the national average Synergy Indices for CO2-PM, CO2-SO2, and CO2-NOx were only 0.02, 0.01, and 0.01, indicating weak synergistic effects between CO2 and air pollutant. This low coordination level is mainly caused by the continued implementation of separate and uncoordinated management frameworks for carbon and air pollutants in most provinces. Furthermore, clean energy substitution was identified as the most effective measure for emission reduction, with potential decreases of 66.45 %, 70.16 %, 70.43 %, and 9.80 % for PM, SO2, NOx, and CO2, respectively. This study provides a practical roadmap for the development of synergistic mitigation policies and offers valuable insights for other countries, such as India, in addressing climate change challenges within the energy sector.