Studies regarding background concentrations of rare earth elements (REEs) are scarce and have mainly focused on a limited number of soil types from the northern hemisphere. The aim of this study was to determine REE concentrations in thirty-five benchmark soils of Brazil. Composite soil samples were taken from areas under native vegetation or with minimal anthropogenic influence. Concentrations of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, Lu, Dy, Er, Ho, Tb, Tm, Y, Sc, and Fe were determined by ICP-OES using a cyclonic spray chamber/nebulizer system after microwave acid digestion. Results were assessed by descriptive statistics, Pearson correlation, and principal component analysis (PCA). Regression analyses among Fe, organic carbon, and REEs were performed to provide a tool for estimating REE concentrations in soils. The REE concentrations in the Brazilian benchmark soils were in the following order: Ce > La > Nd > Pr > Y > Sm > Gd > Sc > Dy > Yb > Eu > Er > Tb > Ho > Lu > Tm. The clear decoupling between light and heavy rare earth elements in soils, indicated by multivariate analysis, is mainly related to differences in parent material. The lowest REE concentrations were found in sandy sediments, whereas the highest REE concentrations were observed in basalt, biotite gneiss, and clayey sediments. The organic carbon and Fe concentrations can properly predict REE concentrations in soils; such a finding can assist in estimating REE concentrations in soils not only in Brazil but also in similar soils developed under tropical conditions.