Abstract: Hexabromocyclododecanes (HBCDs) are globally produced brominated flame retardant (BFR) and are used primarily as an additive FR in thermal insulation building materials, upholstery textiles, and electronics. HBCDs not only pollute the ecological environment, but also harm the health of human beings through the food chain. The study on the environmental fate and biomagnification of HBCDs diastereomers and enantiomers in food chains is an important foundation for risk assessment and effective pollution control. The characteristics of HBCDs, the selective accumulation, biomagnification and transformation of HBCDs diastereomers and their enantiomers in food chain are reviewed in this paper. The influence factors of the selective accumulation and transformation were most likely ascribed to the combined effect of several aspects, including the living and feeding habits, trophic level of organisms, and the selective absorption, metabolism and bioisomerization of HBCDs. Recent research results indicate that the accumulation, transformation and biomagnifications behavior of HBCDs diastereomers and their enantiomers in the ecological system is not a single process, but the result of multiple factors of biological and environmental processes. Further studies will focus on the selective environmental behavior of HBCDs diastereomers and enantiomers in the freshwater and terrestrial food chains and the control influence factors of the selective environmental behavior during food chains transfer, which will provide a scientific basis for the assessment of environmental risks.