Iron oxide-rich colouring materials exhibit substantial diversity across various contexts, encompassing a wide range of physical, chemical, petrographic, and mechanical characteristics. The identification ofthese materials holds the key to understanding exploited mineral resources and the criteria of selections in Palaeolithic societies. Geochemical methods delve into the intrinsic properties of rocks, offering insights into their historical records, including their formation, weathering transformation, and technical applications. Therefore, for the comprehensive collection and analysis of geochemical data pertaining to such archaeological materials, this paper proposes to establish a foundation with diverse iron oxide rich reference materials. This serves a triple purpose: 1) formulation of measurement procedures tailored to the unique physical attributes of iron oxide-rich materials, 2) elucidation of the geological formation and context in relation to material composition, and 3) facilitating comparisons between geochemical analyses conducted on archaeological specimens and compatible geological references, whether local, regional, or extra-regional. The aim is to ensure a consistent basis for comparison. This paper presents a comprehensive investigation of the geochemical composition of seven selected iron oxide-rich reference rocks. The objective is to provide a robust framework for conducting geochemical analyses and statistical data processing on archaeological specimens and relevant reference rocks, leveraging non-invasive Proton-Induced X-ray Spectroscopy (PIXE) data.