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The rapid development of the tourism industry has been accompanied by an increase in CO2 emissions and has a certain degree of impact on climate change. This study adopted the bottom-up approach to estimate the spatiotemporal change of CO2 emissions of the tourism industry in China and its 31 provinces over the period 2000–2015. In addition, the decoupling index was applied to analyze the decoupling effects between tourism-related CO2 emissions and tourism economy from 2000 to 2015. The results showed that the total CO2 emissions of the tourism industry rose from 37.95 Mt in 2000 to 100.98 Mt in 2015 with an average annual growth rate of 7.1%. The highest CO2 emissions from the tourism industry occurred in eastern coastal China, whereas the least CO2 emissions were in the west of China. Additionally, the decoupling of CO2 emissions from economic growth in China’s tourism industry had mainly gone through the alternations of negative decoupling and weak decoupling. The decoupling states in most of the Chinese provinces were desirable during the study period. This study may serve as a scientific reference regarding decision-making in the sustainable development of the tourism industry in China.