The present study investigates legacy and novel brominated flame retardants (BFRs) in atmospheric PM2.5 associated with various urban source sectors in a city and electronic waste (e-waste) recycling facilities in southern China. The concentrations of polybrominated diphenyl ethers (PBDEs) and novel BFRs (∑2NBFRs) at the urban industrial park (UIP) sites varied greatly from 22.0 to 105 pg m-3 and from to 29.7 to 459 pg m-3, respectively, and higher concentrations were generally found at sites involving industrial sectors of electronics, plastics, and machinery. Their spatial variations at other urban potential source sites were small suggesting a lack of strong point emissions. The levels of PBDEs and ∑2NBFRs at the e-waste facilities (220-2356 pg m-3 and 83.6-569 pg m-3) were significantly higher and did not temporally decline, indicating that improvement in e-waste recycling techniques does not significantly reduce emissions of PBDEs. NBFRs dominated the BFRs at the urban sites (55% on average), while PBDEs were still dominant (78%) at the e-waste sites. PBDE congener profiles in PM2.5 were substantially different from those in commercial mixtures. The congener profiles as well as their correlations suggested frequent formation of lower brominated PBDEs from degradation of highly brominated congeners in this region, which became appreciable due to the reduced emissions. The significant correlations among the lower brominated congeners also reflected similar environmental behaviors due to similar physicochemical properties.