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There is scant information on the presence of the polybrominated diphenyl ethers (PBDEs) and other alternative flame-retardants (NFRs) in Africa. Hence, to investigate their levels, sources, and human exposure scenarios, elevated fine dust (EFD) samples from apartments (n = 12), working places (n = 9) and cars (n = 12), floor dust (FD) samples (n = 5) and outdoor dust samples (n = 21) were collected from Alexandria, Egypt, during 2014. Gaseous concentrations were estimated using low density polyethylene sheets (n = 33 and 21 for indoor and outdoor sites, respectively). Indoor gaseous and dust PBDE (7.0–300 pg/m3; 4.0–770 ng/g), and NFR (0.40–48 pg/m3; 0.50–8.5 ng/g) concentrations were significantly higher (p = 0.004–0.02) than outdoor concentrations (PBDEs: 3.0–41 pg/m3, 1.5–195 ng/g; NFRs: 0.20–13 pg/m3, 0.50–4.0 ng/g). Median PBDE concentration in cars (210 ng/g) was higher than in apartments and working places (130  ng/g respectively). PBDE concentrations in FD were 7.0–14-folds lower than EFD concentrations. Outdoor PBDE concentrations were significantly higher (p < 0.01) at residential–industrial places with older buildings. All samples were dominated by BDE-47 and 99. HBB, BTBPE and DDC-CO were the most abundant NFRs in EFD samples. Profiles of PBDE and NFR in FD closely matched those of outdoor dust, indicating a possible carryover from the outdoor environment. Although factors such as number of electronics, construction year and floor type significantly correlated with the majority of PBDE congeners and some NFRs in apartments and working places, sources were not clearly identified for NFRs. Significant log-linear relationships were obtained between theoretical and calculated dust-air partitioning coefficients for all samples indicating an equilibrium state between dust and vapor. Low possibility of occurrence of adverse health effects was concluded, with the inhalation pathway (for adults) and dust ingestion (for children) acting as the most important exposure routes.