Big Harris Creek, North Carolina, possesses a geomorphic history and alluvial stratigraphic record similar to many drainages in southern Appalachian Piedmont. An approximately 1 km reach of Upper Stick Elliott Creek, a tributary to Big Harris Creek, was used herein to (1) explore the use of chemostratigraphic methods to define and correlate late Holocene alluvial deposits along this relatively uncontaminated rural stream containing legacy sediments (historic, anthropogenically derived deposits), and (2) interpret depositional floodplain processes within small (<10 km2), headwater drainages. The lithofacies within four floodplain sections were described in channel banks and sampled at about 5 cm intervals. The 128 collected samples were then analyzed for grain size and the concentration of 22 elements using X-ray fluorescence. Well-defined chemostratigraphic units (facies) were defined on the basis of a multi-elemental fingerprint using a principal component analysis (PCA) and verified using discriminant analysis (DA). Chemostratigraphic units did not reflect grain size at a site (by design) but marginally correlated to lithofacies defined by field descriptions. Of significant importance, chemostratigraphic units could be quantitatively correlated between the four stratigraphic sections at a much higher spatial resolution (~5 cm) than could be performed using other sedimentologic parameters alone. In combination, the lithostratigraphic and chemostratigraphic architecture of the floodplain is consistent with a previously proposed sequence of deposition for the legacy deposits in which extensive land-use change associated with the onset of cotton farming in the 1860s led to upstream incision and gully formation and downstream deposition on the floodplain surface. Deposition appears to have progressed downvalley as incision deepened, probably in the form of crevasse splay deposits or proximal sandsheets that were occasionally interbedded with vertically accreted sediments. The results indicate that chemostratigraphy represents a highly useful approach to the assessment of floodplain depositional processes over (at least) relatively small temporal and spatial scales, even in areas with minimal sediment contamination.