A survey of copper levels in agricultural soils of central Chile revealed two soil clusters-one with a mean copper level of 162 mg/kg and one with a mean copper level of 751 mg/kg of soil. Samples of soils from both soil clusters were characterized on the basis of physicochemical characteristics, and copper extractability was compared by saturation and CaCl2 extraction as well as an acid-leaching procedure (TCLP). We also measured the copper content of various tissues of tomato (Lycopersicon esculentum) and onion (Allium cepa) crops growing on these soils. Other than copper levels, soils from the two clusters were quite similar, with slightly greater levels of molybdenum and cadmium in the high-copper soils. Within each cluster, extracted copper levels and total soil copper levels were not correlated. However, the three extraction procedures solubilized significantly more copper from the high-Cu soils. Mineralogical characterization of the soil particles and depth profiles of soil metal levels in a subsample of sites suggested that highly insoluble copper ore and mining wastes might account for the high copper levels. Neither total nor extractable copper levels allowed statistical prediction of the levels of copper in plant tissue. The edible tissues of both crops had the same mean copper content, regardless of the copper soil level. However, copper contents of stems and leaves were significantly higher for plants growing on the high-Cu soils. These results show that in these soils, high copper levels are associated with very insoluble copper species and thus low bioavailability of copper to crop plants.