This article demonstrates the accuracy of non-destructive portable X-ray fluorescence (pXRF) for the study of obsidian in central Mexico. Obsidian sources were identified for a sample of 103 artifacts from the site of Xaltocan, which spanned the rise and fall of the Aztec empire and the first centuries of Spanish colonial rule (AD 900–1700). Sources were assigned by comparing pXRF measurements with previously published source data and were verified using the standard techniques of laboratory XRF (lXRF) and instrumental neutron activation analysis (INAA). Additional tests of potentially confounding factors show that neither length of read time, presence of surface residue, nor incomplete detector coverage due to small artifact size compromised our ability to attribute sources to artifacts. Concave surfaces did decrease the accuracy of readings because of the greater distance between the artifact and the detector. Our results provide new insight into the stability of supply networks and markets well into the Colonial period as well as the homogenizing tendencies of the Aztec market system.