Strata of the Champlainian (Middle Ordovician) Decorah Subgroup in the upper Mississippi Valley region have been correlated on the basis of the chemical composition of K-bentonite beds in widely distributed outcrops and cores. The four principal K-bentonite beds in the Decorah—the Deicke, Millbrig, Elkport, and Dickeyville—can be differentiated by their unique chemical fingerprints, which were established using a linear discriminant function analysis. The elements that served as the best discriminators of differences between beds were, in order of atomic number, Na, Sc, Ti, Zr, Sm, Eu, Tb, Dy, Yb, Lu, Hf, Ta, and Th. Although no one element serves to delineate a K-bentonite bed completely from others, a combination of elements can do so. The chemical signatures of the Deicke and Millbrig K-bentonite Beds, the two thickest and most widespread K-bentonites in the Mississippi Valley, were recognized in outcrop and subsurface from southern Minnesota to southeastern Missouri, a distance of about 900 km. The Elkport and the Dickeyville K-bentonites were chemically identified in a limited area in northern Illinois, southwestern Wisconsin, and northern Iowa. The Decorah consists of widespread lithologic units that are approximately parallel to K-bentonite beds in some areas, but in other areas lateral gradation of lithologies, as shown by K-bentonite correlations, indicates contemporaneity of Decorah lithofacies.