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High-speed rail (HSR) serves as a low-carbon-dioxide mode of transportation, and its networked development aligns with the global trend toward green transportation transformation. While some studies have examined HSR’s impact on carbon dioxide reduction, they have tended to overlook its spatial and temporal variations, and lack a comprehensive understanding of its varied mechanisms in different regions. This paper analyses how HSR network development in China affects transport and total carbon dioxide emissions through substitution and spillover effects. The study has the following main findings. (a) The development of China’s HSR network over the past decade has reduced total carbon dioxide emissions by 0.232%, primarily through carbon dioxide savings from industrial restructuring. HSR has also reduced transport carbon dioxide emissions by 0.729%, mainly by substituting highways, conventional rail and civil aviation. (b) The impact of HSR network development on carbon dioxide emissions exhibits regional heterogeneity. The economically developed eastern region has experienced the most significant emission reduction effects, which mainly resulted from both substitution and spillover effects; whereas in central and western China, reductions in transport carbon dioxide emissions and total emissions were mainly driven by the spillover effect and substitution effect, respectively. This research provides scientific guidance for leveraging HSR network development to promote carbon dioxide reduction across different regions.

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