The potential for microbial dechlorination of the weathered polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was determined in sediments with historical contamination by the chlorophenol wood preservative Ky-5 and its associated dimeric impurities. Sediments were collected from four sites of the Kymijoki River in South-Eastern Finland located at 0, 20, 30, and 60 km downstream from the source of contamination, and at a reference site. We examined the congener profiles of historical PCDD/Fs, including non-2,3,7,8-substituted congeners, and determined the dechlorination potential in sediments at the different sites of the river. The measured mean total concentrations for 2,3,7,8-PCDD/Fs were extremely high, 1200 mg/kg dw, at the most contaminated site, Kuusankoski. The mean concentrations for the predominant 2,3,7,8-congeners were 1,2,3,4,6,7,8-HpCDF 780 mg/kg dw, and for OCDF 380 mg/kg dw at Kuusankoski. At all other study sites of the river the mean total concentrations for 2,3,7,8-PCDD/Fs varied between 9 and 96 mg/kg dw, (6-80 mg/kg dw for 1,2,3,4,6,7,8-HpCDF, 3-13 mg/kg dw for OCDF). The sediment PCDD/F composition was similar to that of Ky-5, indicating that no or only minimal biodegradation of PCDD/F congeners has occurred in the river sediments over the last few decades since the contamination events. Microbes capable of PCDD/F dechlorination were present at all study sites based on Dehalococcoides-like Chloroflexi community determination and dechlorination of spiked 1,2,3,4-tetrachlorodibenzofuran. However, no substantial changes in the relative abundances of PCDD/Fs were observed over 2.5 years in laboratory microcosm studies, indicating that anaerobic dechlorination of weathered PCDD/Fs was limited over the course of the experiment. Therefore, concentrations of weathered PCDD/Fs in the sediments of the Kymijoki River are expected to remain at the same level for decades or centuries with further migration towards the Baltic Sea.