We present a new multi-analytical approach to the characterization of black pigments in Spanish Levantine rock art. This new protocol seeks to identify the raw materials that were used, as well as reconstruct the different technical gestures and decision-making processes involved in the obtaining of these black pigments. For the first of these goals, the pictorial mat- ter of the black figurative motifs documented at the Les Dogues rock art shelter (Ares del Maestre, Castello ́ n, Spain) was characterized through the combination of physicochemical and archeobotanical analyses. During the first stage of our research protocol, in situ and non- destructive analyses were carried out by means of portable Energy Dispersive X-Ray Fluo- rescence spectrometry (EDXRF); during the second stage, samples were analyzed by Opti- cal Microscopy (OM), Raman spectroscopy, and Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM-EDX). Two major conclusions have been drawn from these analyses: first, charred plant matter has been identified as a main compo- nent of these prehistoric black pigments; and second, angiosperm and conifer charcoal was a primary raw material for pigment production, identified by means of the archaeobotanical study of plant cells. For the second goal, black charcoal pigments were replicated in the labo- ratory by using different raw materials and binders and by reproducing two main cha¿ınes ope ́ ratoires. The comparative study of the structure and preservation of plant tissues of both prehistoric and experimental pigments by means of SEM-EDX underlines both a complex preparation process and the use of likely pigment recipes, mixing raw material with fatty or oily binders. Finally, the formal and stylistic analysis of the motifs portrayed at Les Dogues allowed us to explore the relationship between identified stylistic phases and black charcoal pigment use, raising new archaeological questions concerning the acquisition of know-how and the transfer of traditionally learned cha¿ınes ope ́ratoires in Spanish Levantine rock art.