Globally, soil acidification is becoming a serious environmental and ecological concern, posing a major threat to ecosystem functions and services. In order to clarifying the acidification mechanism, evaluating acidification risk, and reconditioning soil acidification, the effects of acidification on clay mineral composition and soil surface properties should be evaluated. In this study, the surface charge, specific surface area (SSA), species and content of clay minerals were investigated using the ion adsorption method, methylene blue method, and X-ray diffraction (XRD) for brown soil samples, which collected from Muping, Shandong Province, China. The results showed that the clay mineral species and content varied with the degree of acidification. A small amount of montmorillonite was found in weakly acidic soils, and gibbsite was found in strongly acidic soils. Furthermore, although illite, kaolinite, vermiculite, and chlorite were commonly found in soils with different acidification degrees, their content differed. The negative charge (CEC8.2), permanent negative charge (CECP), variable negative charge (CECV), and SSA values decreased with increasing acidification, while anion exchange capacity values (AEC) decreased. The change of CECV was caused by soil organic matter, and the change of CECP was caused by illite content, which accounted for the largest proportion in clay minerals of brown soil.