The Lijiang River is a typical karst river of southwestern China. Karst-aquifer systems are more vulnerable to contamination compared to other types of aquifers. The occurrence and distribution of organochlorine pesticides (OCPs) in surface sediments from the Lijiang River were investigated to evaluate their potential ecological risks. The total concentrations of them in sediments ranged from 0.80 to 18.73 ng/g dry weight (dw) (mean 6.83 ng/g dw). The residue levels of OCPs varied in the order of HCB > HCHs > DDTs. Compositional analyses of OCPs showed that HCHs and DDTs were mainly from historical usage. The ecological risk assessment suggested that HCHs and DDTs in Lijiang River sediments may cause adverse ecological risks, particularly at sites near agricultural areas.