In the present work, more than one hundred and thirty lithic artefacts rediscovered in several archaeological sites dating from the Upper Palaeolithic to the Middle Ages from Calabria (Southern Italy) were petroarchaeometrically characterised through minimally invasive techniques. In more detail, 110 specimens were found in the Grotta della Monaca site (Sant’Agata di Esaro), and the other 23 belong to a collection kept in the Museo Nazionale Preistorico ed Etnografico “Luigi Pigorini” (Roma), coming from several localities (Longobucco, Spezzano della Sila, Cicala, Gimigliano, Roccaforte del Greco, and Bova). For preservation needs, 2 small axes in polished stone and 2 obsidians collected from Grotta della Monaca were analysed by absolutely non-destructive techniques. Optical and electron microscopic investigations, sometimes integrated with wavelength-dispersive X-ray fluorescence spectroscopy and X-ray diffraction spectrometry, allowed us to ascertain that the source area of all the lithic tools was in Calabria, except for obsidians, which come from the island of Lipari (Messina, Southern Italy). For a small number of particularly favourable cases, it was possible to define with great precision the outcrop area of the used rocks given their textural and mineralogical features. The specific source area contained a pickaxe originating from Cetraro–Fuscaldo metabasalt (lawsonite–albite facies) outcrops and two small axes in polished stone, one derived from migmatitic metapelites from Palmi and the other from meta-ultramafic rocks from Curinga. The choice of the used lithologies, harder or softer, had to be linked to the use that humans had to make of the lithic artefacts.