Hexabromocyclododecanes (HBCDs) are now emerging ubiquitous contaminants due to their wide usage, persistence and toxicities. To investigate the bioaccumulative characteristics of HBCDs, sediments, Winkle (Littorina littorea), crucian carp (Carassius carassius) and loach (Misgurnus anguillicaudatus) were collected from two streams near an E-waste dismantling site in China, and HBCD exposure test was then conducted on Chinese rare minnow. The concentration of HBCDs was 14 ng g⁻¹ dry weight in sediments, 186, 377 and 1791 ng g⁻¹ lipid weight in winkle, crucian carp and loach, respectively. γ-HBCD was found to be the dominant diastereoisomer in the sediments (63% of total HBCDs). However, α-HBCD was selectively accumulated in the biotic samples and contributed to 77%, 63% and 63% of total HBCDs in winkle, crucian carp and loach, respectively. Moreover, an enrichment of (−)-enantiomers of α- and γ-HBCD were found in the winkle. The reverse results were observed in the crucian carp and loach. Similar observations of diastereoisomeric and enantiomeric composition were obtained in Chinese rare minnow with those found in the crucian carp and loach. These results indicate that the freshwater species from the streams are contaminated by HBCDs. α-HBCD can be selectively accumulated in organisms and the accumulative characteristics are enantioselective among species.