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Numerous studies have established the link between the built environment and travel behavior. However, fewer studies have focused on environmental costs of travel (such as CO2 emissions) with respect to residential self-selection. Combined with the application of TIQS (Travel Intelligent Query System), this study develops a structural equations model (SEM) to examine the effects of the built environment and residential self-selection on commuting trips and their related CO2 emissions using data from 2015 in Guangzhou, China. The results demonstrate that the effect of residential self-selection also exists in Chinese cities, influencing residents’ choice of living environments and ultimately affecting their commute trip CO2 emissions. After controlling for the effect of residential self-selection, built environment variables still have significant effects on CO2 emissions from commuting although some are indirect effects that work through mediating variables (car ownership and commuting trip distance). Specifically, CO2 emissions are negatively affected by land-use mix, residential density, metro station density and road network density. Conversely, bus stop density, distance to city centers and parking availability near the workplace have positive effects on CO2 emissions. To promote low carbon travel, intervention on the built environment would be effective and necessary. 相似文献