Surface soil and river sediment samples were collected from the downstream of Chuhe River basin, East China, to investigate the occurrence and accumulation characteristics of legacy and novel brominated flame retardants (NBFRs). The respective concentrations of BDE-209 and nine NBFRs ranged from n.d. to 41.4 ng/g dry weight (dw) and from 0.35 to 362.78 ng/g dw in the collected surface soil samples and ranged from 0.29 to 19.73 ng/g dw and from 0.70 to 66.83 ng/g dw in the collected river sediment samples. Soil samples exhibited a higher potential to accumulate BTBPE while the relative abundance of PBT in the collected sediment samples was significantly higher than that in soils. Even so, BTBPE was the predominant NBFR in both soil and sediment samples. The concentrations and relative abundances of legacy and NBFRs exhibited large spatial variation. The calculated concentration ratios of the total of the nine NBFRs (∑9NBFRs) to BDE-209 (∑9NBFRs/BDE-209) in most of the analyzed samples far exceeded 1, implying a clear shift from legacy brominated flame retardants to NBFRs in the downstream of Chuhe River basin.