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Little is known about the presence of organophosphate flame retardants (OPFRs) as a substitute for polybrominated diphenyl ethers in developing countries. This study investigated - for the first time - concentrations, sources and exposure levels of OPFRs in the indoor and outdoor environments of Alexandria, Egypt, in dust and gas-phase samples. Passive samplers were deployed (n = 78) to determine gaseous concentrations, and various dust samples were collected from apartments (n = 25), working places (n = 14), cars (n = 18), and outdoors (OD, n = 30). Indoor concentrations (air: 7.0–64 pg/m3; dust: 150–1850 ng/g) were significantly higher than outdoor (2.0–16 pg/m3 and 83–475 ng/g) concentrations. Tris-1,3-dichloropropyl phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri (2-butoxyethyl) phosphate (TBOEP) and triphenyl phosphate (TPHP) dominated in all samples with more indoor variabilities. Profiles of OPFRs in OD and floor dust (collected from carpets and floors) were similar but differed from elevated fine dust (collected 1 m above the floor from all available surfaces), possibly due to the influence of carryover of OD by shoes. Despite the high uncertainty in dust – air partitioning coefficients, log transformed values showed significant linear relationships with log octanol – air-partitioning coefficients in all microenvironments, indicating an equilibrium partitioning between dust and vapor. Exposure assessment indicated the importance of the dermal exposure route for adults and ingestion route for children.