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• Spectroscopy for non invasive investigation. • Pigments for pottery during Neolithic. • Technology of pottery production by Infrared Spectroscopy. The Neolithic painted pottery, spread all over southern Italy, is considered as an important chronological indicator for the development of VI-V millennium BC prehistoric settlements and cultural traditions. The goal of this work is to contribute to the study of this ceramic class through the chemical characterization of some samples coming from the Aeolian Islands. 16 different sherds have been selected and the pigments preserved in their decorations analyzed via non-invasive techniques: Fiber Optical Reflectance Spectroscopy (FORS), X-ray Fluorescence (XRF), Raman Spectroscopy and Infrared Spectroscopy (FT-IR). The different pigments, some of which no longer clearly visible to the naked eye (red ochre and raw umber) were identified, while the FT-IR data provided information about the pottery differentiation. [ABSTRACT FROM AUTHOR]