We studied the co-occurrence of OPEs and other constituents in atmospheric particles at the two edges of the Mediterranean Sea, under the influence of the transport of polluted air from Europe and dust from the Sahara. The highest OPE concentrations were observed during the summer period in the East Mediterranean and in spring for the NW Mediterranean. The total average atmospheric concentration of Σ6OPEs in the NW Mediterranean was 2103.3 ± 2019.6 pg m−3 (n = 23) with EHDPP and TCPP to be the predominant OPEs, accounting on average for 46% and 37% of the total Ʃ6OPEs concentrations, respectively. The average concentration of Σ6OPEs in East Mediterranean was 156.4 ± 170.3 pg m−3 (n = 67) with TCPP showing the highest concentration (116.1 ± 92.8 pg m−3), followed by TCEP (67.5 ± 55.8 pg m−3). In both areas, OPEs were mostly associated with fossil fuel combustion and road traffic, while the air masses from Saharan desert influenced the concentration of EHDPP, TCEP in NW Mediterranean and the TCEP concentration levels in the East Mediterranean. The total annual deposition of reported OPEs to the Mediterranean basin was estimated to be 584 tonnes, accounting for about 8.5% of the total deposited anthropogenic phosphorus.