Hexabromocyclododecanes (HBCDs) are a class of widely used brominated flame retardants (BFRs) that exhibit strong hydrophobicity. The ubiquity and persistence of HBCDs in sediment have attracted significant attention because of public health concerns. The environmental fate and ecological risks of HBCDs closely depend on their phase distribution in sediments. However, little information is available regarding the freely dissolved concentrations (Cfree) of HBCDs in sediment porewater. In this study, we developed a method to measure Cfree of HBCDs in sediment porewater using triolein-embedded cellulose acetate membranes (TECAM). The TECAM-to-water partitioning coefficient (log KTECAM) was 4.69, 4.77, and 4.63 for α-HBCD, β-HBCD, and γ-HBCD, respectively. In sediments, HBCDs sorbed to the sediment solid phase accounted for more than 99% of the total chemical mass. The dissolved organic carbon (DOC)-water partition coefficient (KDOC) values were derived from TECAM measurements, and the log KDOC values ranged from 5.77 to 6.23 for the three HBCD diastereomers, suggesting a strong tendency for HBCDs to sorb to DOC. The high sorption of HBDCs for DOC implies a potential for DOC-facilitated transport which may enhance the environmental mobility of HBCDs.