The concentrations of three currently used non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and tetrabromobisphenol A bis (2,3-dibromopropyl ether) (TBBPA-DBPE), were examined in environmental and biota samples collected from the Pearl River Delta (PRD) and an electronic waste (e-waste) area in southern China. We also examined deca-BDE (decabromodiphenyl ether) and nine tri- through hepta-BDE congeners for comparison. The results indicate that these non-PBDE BFRs occur widely in the environment of the two study areas. We found a noticeable increase in the levels of TBBPA-DBPE and DBDPE in recent sediments, the concentrations of which even exceed those of BDE209 (deca-BDE) in some samples from the PRD. The BFR profiles of the two study areas are distinct. Relatively high proportions of DBDPE and TBBPA-DBPE were found in the PRD environment, whereas the levels of discontinued BFRs (penta-BDEs and BDE183) and BTBPE were higher in the e-waste area. Our results suggest that the industrial activities in the PRD and the recycling of e-waste have introduced distinct types of BFR contamination to the ambient environment and deca-BDE product has been partly replaced by the TBBPA-DBPE and DBDPE in the PRD. Furthermore, BTBPE and DBDPE were detected in bird tissues and BTBPE in the fish tissues collected from the e-waste area. This is the first report of the occurrence of TBBPA-DBPE in environmental samples worldwide. More studies are needed for reaching a better understanding of the behavior, bioaccumulation, and toxicology of these increasingly used BFRs in the environment.