This paper expanded the Logarithmic Mean Divisia Index (LMDI) model through the introduction of urbanization, residents’ consumption, and other factors, and decomposed carbon emission changes in China into carbon emission factor effect, energy intensity effect, consumption inhibitory factor effect, urbanization effect, residents’ consumption effect, and population scale effect, and then explored contribution rates and action mechanisms of the above six factors on change in carbon emissions in China. Then, the effect of population structure change on carbon emission was analyzed by taking 2003–2012 as a sample period, and combining this with the panel data of 30 provinces in China. Results showed that in 2003–2012, total carbon emission increased by 4.2117 billion tons in China. The consumption inhibitory factor effect, urbanization effect, residents’ consumption effect, and population scale effect promoted the increase in carbon emissions, and their contribution ratios were 27.44%, 12.700%, 74.96%, and 5.90%, respectively. However, the influence of carbon emission factor effect (−2.54%) and energy intensity effect (−18.46%) on carbon emissions were negative. Population urbanization has become the main population factor which affects carbon emission in China. The “Eastern aggregation” phenomenon caused the population scale effect in the eastern area to be significantly higher than in the central and western regions, but the contribution rate of its energy intensity effect (−11.10 million tons) was significantly smaller than in the central (−21.61 million tons) and western regions (−13.29 million tons), and the carbon emission factor effect in the central area (−3.33 million tons) was significantly higher than that in the eastern (−2.00 million tons) and western regions (−1.08 million tons). During the sample period, the change in population age structure, population education structure, and population occupation structure relieved growth of carbon emissions in China, but the effects of change of population, urban and rural structure, regional economic level, and population size generated increases in carbon emissions. Finally, the change of population sex structure had no significant influence on changes in carbon emissions.
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