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This paper uses the carbon emissions trading pilot study of 2013 as a quasi-natural experiment, combined with panel data of 30 provinces and cities in China during 2000–2017, and applies the difference-in-difference (DID) model to investigate the specific impact and mechanism of the carbon emissions trading scheme (ETS) on energy efficiency. The results, which and passed a series of robustness tests, showed that the carbon ETS can significantly improve single-factor energy efficiency and total-factor energy efficiency. The effect mechanism test showed that the carbon ETS can improve energy efficiency by promoting technological innovation of enterprises, and that the marketization level enhanced the carbon ETS's promotion of energy efficiency. Furthermore, this study measures the energy rebound effect at the macro level in China. The results showed that the average energy rebound effect in China is 79.94%. Once the carbon emission trading pilot work was officially launched, the energy rebound effect of the pilot provinces was significantly higher than that of the non-pilot provinces, and the energy conservation effect of the carbon ETS did not function as expected. The research conclusions of this paper provide empirical evidence and policy inspiration for China to improve energy efficiency and accelerate the process of energy conservation.