【Objective】 Soil surface is the main place for various chemical and biochemical processes in soils and most of the negative charges are concentrated here. The five electrochemical characteristics, surface potential, surface charge density, surface electric field strength, specific surface area, and surface charge, deeply affect a series of physical and chemical processes in soils. Therefore, an accurate understanding of the electrochemical properties of soil surface has extensive and profound significance for the prevention and control of soil erosion, soil management and regulation, vegetation restoration and reconstruction in karst areas. However, it is still unclear how soil surface charge properties evolve with environmental factors change in different succession stages of rocky desertification.【Method】 In this study the method of combined analysis of surface properties was applied to measure surface potential, surface charge density, surface electric field strength, specific surface area, and surface charge of the soils varying in different rocky desertification grades in Anshun area. Correlation and redundancy analyses were used to explore the effects of soil environmental factors on its surface electrochemical properties. 【Result】 Soil surface charge density, surface electric field strength, specific surface area, and surface charge decreased with the increase in rocky desertification intensity, and the variation range was 0.34 C·m^–2～0.42 C·m^–2, 4.85×10⁸ V·m–1～5.86×10⁸ V·m–1, 47.11 m²·g^–1～ 53.16 m²·g^–1, 16.86 cmol·kg^–1～22.82 cmol·kg^–1, respectively. Also, the soil surface potential increased with the increase in rocky desertification intensity and the variation range was –113.74 mV～–115.10 mV. Soil clay, sand, amorphous alumina, and humic acid were the main factors affecting soil surface electrochemical properties change, and the interpretation rates were 48.3%, 38.1%, 13.0% and 12.0%, respectively. The effects of soil particle size composition, organic matter composition, and metal oxides on soil surface electrochemical characteristics were as follows: soil clay > sand > silt, humic acid > organic carbon > fulvic acid, and amorphous alumina > free iron oxide > amorphous iron oxide. 【Conclusion】 Our study revealed that during the succession of karst rocky desertification, soil physical properties, chemical properties, and oxide content changed significantly, and this led to changes in soil surface electrochemical properties.