With the panel data of 30 provinces and municipalities of China from 2006 to 2016 and with industrial structure as spillover channels, this paper studies the impact of outward foreign direct investment (OFDI) on the emission of CO2 in China. The results show that by exerting impact on industrial structure, OFDI hinders the effect of rationalization of industrial structure on the emission of CO2 while strengthening the role of superiority of industrial structure in accelerating the emission of CO2. In China’s eastern region, through rationalization of industrial structure and upgrading of industrial structure, OFDI has promoted the emission of CO2. In central region, OFDI has also exerted positive impact on CO2 emission through industrial structure while only its impact through rationalization of industrial structure has the statistical significance but the influence of the superiority of industrial structure on the carbon dioxide emission is not significant. In western region, although the impact of OFDI through industrial structure on CO2 is positive, there is no statistical significance for the two of them. Therefore, this paper holds the idea that under the background of China’s open, shared and green development, more attention ought to be paid to the overall effect of OFDI on the domestic ecological environment, especially on industrial structure and carbon emission at home, so as to boost China’s green development.