This paper discusses the occurrence and spatial distribution of metals and persistent organic pollutants (POPs: including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), Polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs) in sediments from a river-reservoir system. Surface sediments were sampled from thirteen sites of the Congo River Basin and Lake Ma Vallée, both situated in the vicinity of the capital city Kinshasa (Congo Democratic Republic). Sediment qualities were evaluated using toxicity test based on exposing Ostracods to the sediment samples. The highest metal concentrations were observed in sediments subjected to anthropogenic influences, urban runoff and domestic and industrial wastewaters, discharge into the Congo River basin. Ostracods exposed to the sediments resulted in 100% mortality rates after 6 d of incubation, indicating the ultimate toxicity of these sediments as well as potential environmental risks. The POPs and PAHs levels in all sediment samples were low, with maximum concentration found in the sediments (area of pool Malebo): OCP value ranged from 0.02 to 2.50 with POCPs: 3.3 lg kg_1; PCB ranged from 0.07 to 0.99 with Total PCBs (P7 _ 4.3): 15.31 lg kg_1; PAH value ranged from 0.12 to 9.39 with PPAHs: 63.89 lg kg_1. Our results indicate that the deterioration of urban river-reservoir water quality result mainly from urban stormwater runoff, untreated industrial effluents which discharge into the river-reservoirs, human activities and uncontrolled urbanization. This study represents useful tools incorporated to evaluate sediment quality in river-reservoir systems which can be applied to similar aquatic environments.