The synchrotron characterisation of archaeological and heritage materials has undergone a steep development in the past years, among a range of the other advanced characterisation techniques. For synchrotron techinques alone, close to a hundred articles were published in 2011 on such materials, prompting new developments at large scale facilities. However, few publications have discussed the specific characteristics of heritage materials in their advanced spectroscopic and imaging study. here, we suggest that a greater consideration be put on the specificities of ancient materials and their theoretical implications on the analytical process. In particular, we discuss the importance of the a posteriori framework of the study of heterogeneous materials considered in their historicity as structuring parameters of their study. Major implications are the relevance of trace analyses, those of majors and we suggest, more importantly, the dynamics between both endopoints. The on-going development of ultimodal spectral imaging appears as a way to better address corresponding difficulties. Epistemologically, we suggest that a reflexive approach be developed to explain, structure and possibly contribute to narrowing down the field of possible methodological research.