Chloroanisoles (CAs) in the environment are mainly derived from chlorophenols and other chlorinated hydrocarbons with similar structures. As molluscicide, pentachlorophenol was released to the schistosomiasis area of Lake Dongting watershed in China and caused CAs pollution. This study aims at quantifying the pollution characteristics and potential risks of chloroanisoles in surface waters and sediments of three tributaries, the Lishui River (LS), the Ouchihe River (OCH) and the Tuojiang River (TJ) of Lake Dongting. Gas chromatography-mass spectrometry was used to measure the concentration of CAs. Results show that:(1) Water is the main sink for CAs. The CAs concentrations in surface water of the three river shows significant differences with each other. The water pollution level from high to low was LS > OCH > TJ, with CAs concentration being 18.94, 8.83 and 4.14 ng/L, respectively. There is no significant difference in total CAs content in the sediments of the three tributaries, with CAs content being 2.86, 3.61 and 4.07 ng/g, respectively. (2) Trichloroanisole (TCA), tetrachloroanisole (TeCA) and pentachloroanisole (PCA) were the main pollutants of LS both in surface water and sediments (73.75% and 68.89%, respectively). The proportion of chloroanisole (CA) and dichloroanisole (DCA) in the surface water of OCH is relatively higher than other CAs (both, 48.59%), while in sediments TCA, TeCA and PCA were the main pollutants (the three, 93.38%); The CAs in the surface water and sediments of TJ were dominated by CA, accounting for 28.26% and 75.56%, respectively. (3) From upstream to downstream, the CAs in the surface water of LS showed a downward trend, while in the sediments increased slightly; the CAs in the surface water of OCH showed a downward trend, and the content of CAs in the sediments did not have significant trend; in TJ, only CA in water and sediments fluctuating rose, while other CAs had fluctuations but no significant changes. (4) PCA concentration in the water was lower than the acute 50% lethal concentration for fish and invertebrates reported in previous studies. There was no serious impact on aquatic organisms so far, however, the risks of CAs to the human health and environment could not be ignored.