Ionoluminescence (IL) has mainly been used to detect impurities or defects inside synthetic materials. This paper gives a summary of new applications of IL to natural minerals that might be found in ancient pieces of jewellery or decorative artefacts (affreschi, stucchi, mosaics). Some relevant examples of its use for archaeometrical purposes are given to highlight the potential of the technique. Chemical information can be obtained by luminescent characterization of minerals. IL spectra act as digital imprint for elements or defects inside each material, enabling differentiation of natural specimens from imitations and/or synthetic analogues. Crystal field theory indicates it is the coordination number of the emitter inside the crystalline structure that gives information on its valence. Historical confusion between rubies and red spinel can easily be resolved by analysis of IL spectra. Modern synthetic diamonds can also be discriminated and blue sapphire can be distinguished from blue kyanite, a silicate that is currently being sold as its imitation. The technique can also differentiate between the synthetic and the natural gems. Polymorphs can be identified, and it is possible to recognize minerals from isomorphic series (from the same chemical group with the same structure) even when they share the same light emitter (e.g. Mn(2+), in carbonates). High-quality glasses (e.g. laser glasses) which are normally used for faking gemstones can be also detected. We fully believe IL will, in the future, be a powerful technique for determining the crystallinity of solids. This paper gives an overview of possible applications of IL to archaeometry for mineral characterization; this is a new application that still requires further study.