Carbon black materials have been frequently used from prehistory as pigments for drawings and paintings and also as dyes, inks and cosmetics, since they are easy to make by burning organic matter. However, the carbonaceous phases they form are often ill-ordered and not easy to characterize. Five carbon black Roman micro samples found in vessels in houses in Pompeii were studied. These precious powders correspond to mixed phase samples that contain both crystalline and ill-ordered components. Here, a methodological approach that accomplishes the identification, quantification and mapping of the different phases in these heterogeneous samples using synchrotron-based techniques is proposed. The results were compared with those from scanning electron microscopy. Information about the nature of the mixtures and the origin of carbon black pigments is obtained. The use of charred vegetable materials is concluded, independently of the shape and the nature of the container.