Organophosphate esters (OPEs) are novel ubiquitous contaminants that are attracting growing concern, but their emissions into the environment are still poorly understood. In this study, 12 OPEs were measured in fine particulate matter (PM2.5) at 20 industrial sites in an urban region and four e-waste recycling facilities in a rural region in southern China. There was no significant difference in the concentrations of ∑OPEs between the urban region (519–62,747 pg/m3, median = 2854 pg/m3) and the rural e-waste region (775–13,823 pg/m3, 3321 pg/m3). High OPE concentrations in urban PM2.5 were generally associated with the electrical, electronic, plastic, and chemical industries. There were no significant correlations between most OPEs in these two regions, suggesting different emission mechanisms. The average emissions of ∑OPEs estimated using a simplified dispersion model were 73.0 kg/yr from the urban industrial point sources and 33.2 kg/yr from the e-waste recycling facilities. The estimated emission inventory from industrial activities in the whole city (3228–4452 kg/yr) was approximately 30-fold higher than that from the e-waste recycling (133 kg/yr) facilities because urban region has a much larger industrial scale. To the best of our knowledge, this is the first effort to model the emissions of OPEs from industrial and e-waste recycling activities to the atmosphere.