Polycyclic aromatic hydrocarbons (PAHs) are a group of aromatic hydrocarbons with serious toxic effects on ecosystems and human health. In this study, Lipu River Basin in a typical karst area was selected as a case to study the influence of anthropogenic activities on the distribution and fate of PAHs in surface water. The results showed that 16 priority controlled PAHs were detected in all samples. PAHs discharges from industrial activities were the primary pollution sources, and the non-point sources such as traffic emission, biomass combustion and surface runoff with agricultural origin also contributed to the high PAHs concentrations. The coexistence of multiple PAHs posed a high risk to the aquatic organisms and human health. The quality of surface water was continuously improved, but water pollution problems remain. The results of this study provide valuable theoretical support for environmental protection and policy making.