Typical halogenated persistent organic pollutants (Hal-POPs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs), and dichlorodiphenyltrichloroethane (DDT), are a group of ubiquitous organic pollutants with an endocrine disrupting effect. This study evaluated the accumulation and congener profiles of Hal-POPs in the bodies of men who live/work in areas of South China where electronic wastes are collected and managed, especially in their semen samples. The results show that the detection frequency and serum concentrations of Hal-POP congeners within the high-exposure group (HEG) were higher than those of the low-exposure group (LEG). Furthermore, an identical trend was observed for the seminal plasma concentrations of Hal-POPs. The distribution characteristics, such as their mean, median, and discrete values, of PBDE congeners in serum and semen samples from the same subjects were consistent with each other. However, the distribution characteristics of PCB congeners in serum samples were different from those in semen samples. BDE153 was one of the most abundant congeners found in the serum and semen samples; hence, it can be identified as an indicator PBDE congener. Further research is needed to explore the mechanism of Hal-POPs distribution in human semen and serum samples.