Exploring the hydrogeochemistry of cave drip water and its response to precipitation events in karst rocky desertification regions is of great significance to the paleoenvironment reconstruction of the karst desertification process using speleothem. We selected three perennial drip sites in the Shijiangjun Cave, located in Guizhou Province, Southwest China, and carried out high-frequency monitoring and sampling during two rainfalls from 22 to 25 May 2016. The major hydrogeochemical parameters of drip water and their relationships with karst desertification were analyzed. The results show that the hydrogeochemistry of the drip water in the Shijiangjun Cave, characterized by HCO3-Ca·Mg, was dominated by the dissolution of calcareous dolomite. The three drip sites were classified into the delayed response type (W1) and the rapid response type (W2 and W3) based on the response speed of the drip water indicators to precipitation, which were highly influenced by the piston effect and precipitation dilution, respectively. Furthermore, the response sensitivity of the drip water indicators to precipitation was constrained by the desertification degree in the rainy season, specifically, the faster response appeared in the higher desertification degree area. It is essential to select appropriate drip sites and establish an applicable indicator system for the evolutional history reconstruction of karst desertification using speleothems.