High volume air samples were collected from April 2016 to March 2017 at five locations across the Beijing-Tianjin-Hebei (BTH) region, to investigate the atmospheric occurrence of organophosphate esters (OPEs). The mean atmospheric concentrations of ∑8OPEs (gas and particle phases) varied from 531 ± 393 pg/m3 to 2180 ± 1490 pg/m3 with the highest level observed at the urban sampling site in Tianjin City. ∑8OPEs were predominated by the chlorinated OPEs (TCEP, TCPP, and TDCIPP), which accounted for 60% ± 16% of the OPE concentrations across the BTH region. Generally, higher levels of gaseous OPEs were found in summer, while higher levels of particle-bound OPEs were observed in winter. The concentrations of gaseous OPEs were positively and significantly correlated with local temperatures (p < 0.05) and relative humidity (p < 0.01), while significantly positive correlations were found between concentrations of particle-bound OPEs and total suspended particulates (TSP) (p < 0.01). These findings confirmed that temperatures, relative humidity and levels of TSP are the main drivers for OPE distributions in different seasons and areas. Gas/particle partitioning of OPEs was also investigated based on the absorption-partitioning model (octanol-air partitioning coefficient (Koa) -based model) and Junge-Pankow adsorption-partitioning model (J-P model). Koa-based model generally showed a better performance in comparison with the measured results. The assessment of inhalation exposure risks indicated that relatively higher exposure risks were found in the urban areas, in particular, in Tianjin City (a median value of the estimated daily intake (EDI) of 106 pg/kg body weight/day), suggesting that more attention should be drawn to OPE distributions in the heavily industrialized megacities. Copyright © 2018 Elsevier Ltd. All rights reserved.