Polybrominated diphenyl ethers (PBDEs) are a class of the emerging persistent organic pollutants that have shown potential harmful effects in in-vivo and human studies. Our goal was to investigate 30 airborne PBDEs in day-to-night or indoor-to-outdoor in three vehicle dismantling factories located in southern Taiwan to assess worker risks. Thirty PBDEs including BDE-7, 15, 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 139, 140, 153, 154, 156, 183, 184, 191, 196, 197, 203, 206, 207, 208, and 209 were analyzed using high-resolution-gas chromatography/high-resolution-mass-spectrometer. Levels of airborne Σ30PBDEs were 275, 336, 200 and 494 p gm–3 in indoor daytime, indoor nighttime, outdoor daytime, and outdoor nighttime, respectively, and their differences were not significant. BDE-209 was the predominant congener among the 30 PBDEs consisting of 82.5–97.9% of Σ30PBDEs in both indoor and outdoor air. Pollution characterizations of the PBDE patterns were similar in air samples except for the outdoor air in the nighttime. Diurnal variations in PBDEs in both indoor and outdoor air were not observed. A principal component analysis was used to test for possible sources of PBDE contamination. BDE-209 in outdoor air was possibly contributed from PBDEs in indoor air, particularly from BDE-209. Characteristics of diurnal PBDE contamination in indoor and outdoor air in vehicle dismantling factories were linked to commercial technical OctaBDE (Bromkal 79-8DE) and DecaBDEs (Bromkal 82-0D and Saytex 102E) mixtures. The highest PBDE intakes of workers via inhalation were assessed as 41.8 and 32.7 pg kg–1 bw day–1 for male and female adults, respectively. It was hypothesized that airborne PBDEs in indoor factories are released from the surface of DecaBDE or OctaBDE technical formulations and influence outdoor air through ventilation or natural dispersion. However, occupational exposure through inhalation might be an important PBDE contamination pathway, but it is minor compared to PBDE dietary intake.