The purpose of this paper is to emphasize the benefits of adopting non-destructive energy dispersive X-ray fluorescence (ED-XRF) as a first-order technique to determine chert whole-rock geochemistry for archaeological sourcing. Chemical signatures for the Touladi and La Martre prehistoric quarries from the lower St. Lawrence and GaspÃ© Peninsula region of Quebec, Canada, are determined and serve as references to test the provenance of regional chert artifacts. Chert experimental flakes, created from quarry geological hand samples, are analyzed and used to validate the method. Archaeological flakes and tools recovered from three archaeological sites are analyzed and tested against quarry samples. Geochemical diagrams and Principal Component Analysis are used to establish artifact-quarry relationships. The effects of surface weathering on the geochemical analysis of archaeological chert artifacts are presented. Sample restoration and research avenues are discussed and proposed to further enhance the robustness of future chert geochemical data sets.