As a result of the limited application of portable X-ray fluorescence (pXRF) in archaeological research in Japan it is necessary to compare this technique to proven, laboratory-based, analytical techniques. In this study instrumental neutron activation analysis, inductivelycoupled plasma mass spectrometry, and electron probe microanalysis are used to validate pXRF and determine the overall suitability of this technique for archaeological obsidian provenance studies in Hokkaido, northern Japan. Furthermore, the results of this study are compared to previously published data to assess reproducibility and compatibility. This study demonstrates the reliability of pXRF for the rapid characterization of Hokkaido obsidian while contributing to the ongoing evaluation of the applicability of ‘‘off-the-shelf’’ pXRF to obsidian provenance research in archaeology.