Power sector is the largest CO2 emitter in China. To mitigate CO2 emissions for the power sector is a tough task, which requires implementation of targeted carbon mitigation policies. There might be multiple forms for carbon mitigation policies and it is still unclear which one is the best for China. Applying a superstructure optimisation model for optimal planning of China's power sector built by the authors previously, which was based on real‐life plants composition data of China's power sector in 2009, and could incorporate all possible actions of the power sector, including plants construction, decommission, and application of carbon capture and sequestration (CCS) on coal‐fuelled plants, the implementation effects of three carbon mitigation policies were studied quantitatively, achieving a conclusion that the so‐called ‘Surplus‐Punishment & Deficit‐Award’ carbon tax policy is the best from the viewpoint of increasing CO2 reduction effect and also reducing the accumulated total cost. Based on this conclusion, the corresponding relationships between CO2 reduction objectives (including the accumulated total emissions reduction by the objective year and the annual emissions reduction in the objective year) were presented in detail. This work provides both directional and quantitative suggestions for China to make carbon mitigation policies in the future.