Six populations of prehistoric Amerindians from Ohio are sampled to establish the relationship of enamel composition and dental caries experience. The populations used included groups practicing hunting-gather-ing-fishing and maize horticulture, and they represent at least two major cultural traditions, the Late Archaic/Glacial Kame (1000–500 BC) and the Fort Ancient and Sandusky Bay Traditions (AD) 1200–1600). Characterization of enamel composition is achieved using scanning electron microscopy energy-dispersive X-ray analysis. Thirteen elements present are quantified, and they are analyzed with respect to each population's subsistence base using correspondence analysis. Evaluations of cariogenic and cariostatic effects of elements are made on the basis of caries frequency comparisons among the populations. Results indicate that zinc, copper, iron, nickel, and calcium-phosphorus ratio distinguish populations exhibiting high, moderate, and low caries frequency as well as discriminate hunter-gatherers from maize horticulturalists.