The path and acting mechanism for the impact of environmental regulation on labor employment are complex, and its practical results have uncertainty and regional difference. Based on the 2003-2017 Chinese provincial panel data, the panel threshold model is constructed with industrial structure as a threshold variable, and the threshold effect of environmental regulation on labor employment is systematically studied. The analysis shows that there is nonlinear impact of environmental regulation on Chinese labor employment, that there are double threshold effects as a whole, that the influence of environmental regulation on labor employment becomes positive from negative when industrial structure level steps across the value of the second threshold, however, the industrial structure level of the majority of coastal provinces does not step across the threshold value, as a result, the increase of environmental regulation will produce negative impact on local labor employment. Thus, We should treat environmental regulation with a development and forward-looking perspective to prevent and reduce the employment risk of environmental regulation. The “double dividends” between environmental protection and employment of environmental regulation can be obtained by accurate administration according to industrial structure level of different places, by reasonably guiding reallocation of the labor under environmental regulation and by actively using policies to raise the skills of the labor and to boost the flowing of labor space.