Arsenic (As) pollutants generated by human activities in karst areas flow into subterranean streams and contaminate groundwater easily because of the unique hydrogeological characteristics of karst areas. To elucidate the reaction mechanisms of arsenic in karst subterranean streams, physical-chemical analysis was conducted by an inductively coupled plasma mass spectrometer and an X-ray fluorescence spectrometer. The results show that inorganic species account for most of the total arsenic, whereas organic arsenic is not detected or occurs in infinitesimal amounts. As(Ⅲ) accounts for 51.0%±9.9% of the total inorganic arsenic. Arsenic attenuation occurs and the attenuation rates of total As, As(Ⅲ) and As(Ⅴ) in the Lihu subterranean stream are 51%, 36% and 59%, respectively. To fully explain the main geochemical factors influencing arsenic attenuation, SPSS 13.0 and CANOCO 4.5 bundled with CanoDraw for Windows were used for simple statistical analysis and redundancy analysis (RDA). Eight main factors, i.e., sediment iron (SFe), sediment aluminum (SAl), sediment calcium (SCa), sediment organic matter (SOM), sediment manganese (SMn), water calcium (WCa2+), water magnesium (WMg2+), and water bicarbonate ion (WHCO3-) were extracted from thirteen indicators. Their impacts on arsenic content rank as: SFe>SCa>WCa2+>SAl>WHCO3->SMn>SOM>WMg2+. Of these factors, SFe, SAl, SCa, SOM, SMn, WMg2+ and WCa2+ promote arsenic attenuation, whereas WHCO3-inhibits it. Further investigation revealed that the redox potential (Eh) and pH are adverse to arsenic removal. The dramatic distinction between karst and non-karst terrain is that calcium and bicarbonate are the primary factors influencing arsenic migration in karst areas due to the high calcium concentration and alkalinity of karst water.