Soil heavy metal contamination poses a serious threat to soil ecosystems and human health. Geochemistry is often used in soil heavy metal contamination research to identify pollution sources, identify elemental cycling mechanisms, and assess the spatial distribution and risk of contamination. However, it is difficult to directly reflect the spatial continuity and deep distribution patterns of contamination. Three-dimensional electrical resistivity tomography (3D ERT) technology often indirectly predicts the distribution of soil contamination by leveraging the electrical structure of the subsurface medium. However, many factors influence this electrical structure, leading to biased predictions. This paper combines geochemistry with 3D ERT technology. A nonlinear statistical model is established based on the geochemical analysis results and resistivity of soil samples. A 3D ERT model is then constructed. This model is used to further investigate the spatial distribution patterns of soil heavy metal contamination and assess the extent of contamination. This study investigated soil sample collection and chemical analysis of heavy metal content at a heavy metal contaminated site in Hunan Province. Antimony contamination was particularly severe in the soil. The 3D ERT data collection and inversion imaging were performed in the soil sample collection area. A 3D ERT model was established to analyze and evaluate the distribution range and extent of antimony contamination in the area. Comparing the antimony content predicted by the model with the actual test data, the results show that the error range is 0.6–16.6%, and the average error is 5.8%. The model has high accuracy, achieving good overall prediction and evaluation results.