The atmospheric concentrations of 14 organophosphate esters (OPEs) were monitored by passive air sampling at 33 sites to determine their spatial distributions, and seasonal variations (summer and winter) in Tianjin, North China. The total concentrations of the OPEs (Sigma 9OPEs) in the summer ranged from 0.08 to 1113 ng/sample with a median of 98.4 ng/sample, which was non-statistically different from the concentrations obtained in the winter (which ranged from 1.93 to 548 ng/sample with a median of 46.2 ng/sample). Among the observed OPEs, the concentrations of TnBP and TCiPP were statistically higher in the summer compared with the winter (p < 0.05). For grouped OPEs, only a significantly higher level of chlorinated OPEs was found in summer than that in winter. In the winter, spatial differences were found to be significantly different between the concentrations of TnBP, TiBP, TCEP, and TEHP in the suburban and rural areas (p < 0.05). Considering the possible point-sources, in the summer, the concentrations of TDCPP, TCiPP, DPEHP, TEHP, and the total concentration of TCPs (denoted as Sigma 3TCP, comprised of the concentrations of TCP, TmCP, and ToCP) in an electronic-waste (e-waste) dismantling area were higher than those obtained at the other sampling sites. Sigma 9OPEs at the e-waste site and another site located near a manufacturing plant of organophosphate flame retardants (OFRs) were both higher than the median concentrations obtained at the other sampling sites, and TCiPP was the most abundant pollutant. In the winter, the concentrations of Sigma 9OPEs at the e-waste site were still higher than their median concentrations at the other sites. Because OPEs are used in aircraft lubricating oils and hydraulic fluids, an airport was thought to be another important source of TiBP and TPhP in the present study. Therefore, the e-waste site, airport, and OFR manufacturing plant may be the major sources of OPEs in the environment.