The health risks of polybrominated diphenyl ethers (PBDEs) to toddlers, children, and adults in creches, nursery schools, cars, and offices in Nsukka, Nigeria, via inhalation, ingestion, and dermal exposure pathways were evaluated. Eight PBDEs congeners (BDE-28, BDE-47, BDE-100, BDE-99, BDE-154, BDE-153, BDE-183, and BDE-209) were determined using gas chromatography-mass spectrometry. This is the first study on PBDEs in creches and nursery schools in Africa. The mean (median) n-ary sumation 8PBDEs (ng/g) in creches, nursery schools, offices, and cars were 4355 (1850), 2095 (1130), and 37741 (2620) respectively. The concentrations of PBDEs between the three microenvironments were significantly different (p < 0.05), and the highest concentration was found in cars. Ingestion of dust was the predominant pathway of exposure to PBDEs for toddlers and children, while dermal absorption was the dominant pathway for adults. Dermal absorption and ingestion in cars, creches, and nursery schools were of the same magnitude. Toddlers with the highest ingestion rate of PBDEs in creches, nursery schools, and cars are at risk especially from prolonged exposure.