The speciation of added plutonium was determined in groundwaters of widely varying composition from four rock types: basalt, granite, shale, and tuff. Plutonium was soluble in the basalt water, which contained a high fluoride ion concentration, probably as a result of its stabilization in solution as fluoro-complexes, primarily of plutonium (IV); it was insoluble, however, in the shale groundwater, which contained the highest concentration of sulfate ion. Results were intermediate in the granite and tuff groundwaters. In synthetic waters containing significant concentrations of both sulfate and fluoride, the effects were smaller and less predictable. Dissolved oxygen, ionic strength, carbonate ion concentration, and pH had little effect on plutonium speciation in the ranges encountered in this study. However, other ionic species not involved in this study may also influence plutonium speciation. The results have potential significance in establishing site-selection criteria for radioactive waste repositories. All other factors being equal, host rocks whose associated waters contain low concentrations of free fluoride ion should be preferable for the location of waste repositories.