As one of the comprehensive exploration techniques for underground geological resources, surface geochemical methods could play an important role in geothermal exploration, which requires detailed and systematic investigations. In this study, we take the Shiba geothermal basin in Huizhou, China, as the research object and apply surface geochemical testing methods to analyze the intrinsic relationship between the geothermal system and the surface soil. The contents of soil gases and elements are mainly determined, among which hydrogen (H2) and radon (Rn) show three obvious negative anomalies, corresponding to three positive anomalies of soil elements (Fe, U, Cr, V, Cu, and As) that are easy to migrate. The largest negative and positive anomalies correspond to the surface above the fault, which is related to the dominant channel from underground to the surface and is caused by the gas loss effect and the dissolution and migration of inorganic ions. However, the effects of the surface environment and organisms cannot be ignored. Only when the geothermal system has a significant impact on a certain geochemical parameter could the anomaly be manifested in the surface soil. Otherwise, most of the geothermal information, including thermal conduction, will be covered by surface factors. After surface geochemical anomalies related to the geothermal system have been identified, anomaly patterns (especially the top anomaly pattern) can be preliminarily established, which can be used for geothermal exploration. Furthermore, based on the empirical regional geothermal formula, the temperature and depth of the Shiba geothermal system are evaluated at 170°C and 4500 m, respectively, indicating that surface geochemical methods have a good practical prospect in the prediction of geothermal resources.