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When did the League of the Five Nations Iroquois originate? This study presents a new approach to answering this age-old question. Compositional data were collected on ceramics (pottery and smoking pipes) from Seneca and Mohawk sites in an attempt to identify and reconstruct exchange and interaction patterns between these two widely separated League members. X-ray fluorescence (XRF) and particle-induced X-ray emission (PIXE) spectrometry were employed to collect data on 15 elements. Using pottery as a baseline for each area, pipe data were utilized in a discriminant-function analysis to identify exotic pipes in Seneca assemblages from different time periods. The investigation focused on pipes because they were a probable item of exchange and because the symbolism of pipes and tobacco made smoking an important part of Iroquoian political protocol. Results showed that Mohawk pipes first occurred in Seneca assemblages sometime between A.D. 1590 and A.D. 1605. This is considered likely to reflect the inception of peaceful political relations between these two groups brought about by the final coalescence of the Iroquois Five Nations Confederacy. The approach developed for this study employed nondestructive analytical techniques applied to common classes of ceramic artifacts. As such, the methodology should be broadly applicable to other studies of interaction and exchange in this and other regions.