This study was carried out in Paraopeba National Reserve. It aims to classify and evaluate the soil of the studied area and to verify the influence of soil attributes on vegetation by testing the following hypotheses: 1) under woodland physiognomies (Cerradão) the soil fertility is higher and the Al content lower; 2) open savanna occurs only in areas with high Al contents. For this purpose, representative soils in the Paraopeba National Reserve were mapped, identified, and samples from five profiles were analyzed. The environmental gradient was easily observed by principal components analyses, where the differences between the sites were highlighted. The Spearman correlation was used to verify the hypothesis. The correlation between vegetation (basal area, density, and richness) and soil (K, Ca2+, and Al3+) was statistically significant. The hypotheses were accepted, but hypothesis 1 only partially. Soil features seem to have an influence on the Cerrado phytophysiognomies and structure. Available phosphorous was an important factor for the maintenance of woodland Cerrado. Also, exchangeable Al3+ plays a major role in the establishment of different Cerrado physiognomies in Paraopeba National Reserve.