Human hair has been widely used as a bioindicator for human persistent organic pollutants (POPs) exposure, but studies on the sources of hair POPs and the relationship between hair and body burden are limited. This study analyzed the possible source apportionment of hair PBDEs and examined the relationship between PBDE concentrations in paired hair and serum from e-waste recycling workers. Using the ratio of BDE 99/47 and BDE 209/207 as indices, we calculated that only 15% of the highly brominated congeners (nona- and deca-BDE congeners) comes from exogenous (external) exposure for both female and male hair, but an average of 64% and 55% of the lower-brominated congeners (tetra- to penta-BDE congeners) come from exogenous exposure for female and male hair, respectively. The higher contribution of exogenous exposure for less-brominated congeners could be related to their relatively lower log KOW and higher volatility than higher-brominated congeners, which make them more readily to evaporate from dust and then to be adsorbed on hair. Higher hair PBDE levels and higher exogenous exposure of less-brominated congeners in females than in males can be attributed to a longer exogenous exposure time for females than males. Significant positive relationships were found in tri- to hepta-BDE congeners (BDE 28, 47, 66, 85, 100, 153, 154, and 183) (R = 0.36-0.55, p < 0.05) between hair and serum, but this relationship was not found for octa- to deca-BDE. Difference in the half-lives between highly brominated congeners and less-brominated congeners could be a reason. This result also implied that we should treat the results of correlation analyses between hair and other organs cautiously.