Chemical quality of fine roots (<1 mm diameter) was determined over a gradient of species composition in the Mixed Mesophytic Forest Region. Ash-free nitrogen, calcium, and phosphorus concentrations of roots declined by 49, 41, and 72%, respectively, over a gradient of increasing soil acidity (pH 5.3 to 4.7). Lignin concentration was unrelated to either the vegetation gradient or any of the soil changes it encompassed; however, astringent phenolics increased by 275% over the same gradient. Trends in the chemical constituency of fine roots suggest that the production of phenolics in below-ground plant parts is increased on nutrient-poor sites. This response is best related to changes in species composition, especially increasing importancy of Quercus spp.