A methodological proposal for the characterisation of dolerite rock aiming to test a non-destructive and non-invasive analytical approach has been developed. Geological samples were collected from several natural outcrops and studied together with seven archaeological stone tools found in a Chalcolithic site of the southern Valencian Community (Spain). The samples were analysed employing portable energy dispersive X-ray fluorescence spectroscopy, Raman microspectroscopy and Fourier transform near infrared spectroscopy. The obtained data were statistically processed in order to evaluate affinities and differences among the geological outcrops and to evaluate the possible provenance of the stone tools. The results of the different techniques were compared and evaluated. The three techniques showed results that were in most of the cases consistent one with each other, suggesting that combining multielement analysis and Raman could be a good way to identify stone tools raw material procurement, being the prior step for the reconstruction of ancient exchange networks.