This soil acidification may increase the bioavailability of copper (Cu) and zinc (Zn) in soils. The objective of this study was to verify the concentrations of Cu and Zn in soils of a vineyard region, including sample acidification, to simulate acid rain. The study was developed in an area of vineyard cultivation, with an adjacent land having other crops grown, in the state of São Paulo, Brazil. Soil samples were collected and GPS located under different uses and coverings. The extracted solutions used to determine the available Cu and Zn forms were diethylenetriaminepentaacetic acid (DTPA), pH 7.3, and calcium chloride 0.01 M. The total forms were obtained by HNO3 digestion. The amounts of Cu and Zn extracted using DTPA were considered high in most of the samples and were greater in the areas cultivated with vineyards that had received fungicide applications for several decades. The total forms were higher in vineyard soils. The amounts of Cu and Zn extracted using CaCl2 did not have good correlation with vineyards or with other metals' forms. The results confirmed that the soil was enriched with Cu and Zn due to the management of the vineyards with chemicals for several decades.