Under the theoretical framework of new structural economics，this paper empirically tests the impact of digital economy on carbon dioxide emissions using a panel data of 91 economies worldwide from 2007—2015 through a double stationary model. The results show that the digital economy has a non-linear effect on CO₂ emissions；when the stage of economic development is used as the threshold variable，the effect of digital economy on CO₂ emission reduction is significantly reduced with the increase of GDP per capita；when the industry structure is used as the threshold value，the higher the degree of matching between the digital economy and the industry structure，the more beneficial to CO₂ emission reduction；in addition，when a economy implements a development strategy contrary to its comparative advantage，it will reduce the development of the digital economy and further lead to an increase in CO₂ emissions. Thus，this paper verifies the development，operation and transformation of the digital economy and CO₂ emissions from the perspective of new structural economics.