The extensive utilization of organophosphate esters (OPEs) has resulted in their widespread presence in the environment, raising concerns about potential human health risks. In this study, 13 OPEs were analyzed in both gas and particle phases as well as in indoor and outdoor atmospheric environments. Moreover, human exposure to OPEs were investigated within a university environment, focusing on forehead contact and individual PM_2.5 inhalation. The results showed similar distribution patterns of OPEs indoors and outdoors, although higher concentrations were found indoors. The average atmospheric concentration of ∑OPEs (combining particle and gaseous OPEs) was 1575 pg/m³ in the outdoor environment and 6574 pg/m³ ∑OPEs in the indoor microenvironments. The overwhelming majority of OPEs exhibit a pronounced propensity to adsorb onto PM_2.5 particles. Notably, the concentration of OPEs on the forehead differed significantly from that in the atmospheric environment, whereas individual PM_2.5 exposure was consistent with the concentration of indoor PM_2.5. Intriguingly, some OPEs with high octanol–water partition coefficient (log K_ow) were not detected in the environment but found on human foreheads. Gas-particle partitioning was predicted using the Harner–Bidleman and Li–Ma–Yang models and the results were in agreement with the monitoring data for approximately half of the OPE monomers. Correlations between OPEs exposure and gas-particle partitioning were found to be more significant for novel OPEs. No non-cancer risk to humans through individual exposure to OPEs was identified via forehead exposure or inhalation. The previously unreported relationship between individual exposure and the environmental occurrence of traditional and novel OPEs demonstrated in this study highlights the importance of evaluating the potential health risks associated with actual OPE exposure.