Polychlorinated dibenzothiophenes (PCDTs) in sediment, soil, and fly ash samples collected in Japan were analyzed and their dioxin-like endocrine-disruption potential and photodegradability investigated. PCDTs were detected in all three types of sample, although the concentrations were lower than those of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). An Ah-immunoassay confirmed that 2,3,7,8-TeCDT, 1,2,3,7,8-PeCDT, 1,2,3,7,8,9-HxCDT, and 1,2,3,4,7,8,9-HpCDT had Ah receptor-binding activities, which means that these PCDTs have the potential to cause dioxin-like endocrine-disruption. Photodegradation of PCDTs by UV irradiation was accompanied by dechlorination. The photodegradation rates of 2,3,7,8-TeCDT and OCDT were lower than the rates for the corresponding PCDF isomers (2,3,7,8-TeCDF and OCDF), which indicates that PCDTs are more stable than PCDFs to photodegradation.