Several spectroscopic techniques have been applied in order to characterize the polychrome pigments used in some religious sculptures, from the 13th to the 18th centuries, belonging to the cultural heritage of Extremadura (west of Spain). First, two energy‐dispersive X‐ray fluorescence portable devices were used. The measurements were carried out in situ, where the artworks were been restored. In addition to these nondestructive analyses, various samples with a millimeter size were taken from some of the sculptures and embedded in polyester resins. The stratigraphy of these fragments was observed through an optical microscope. Finally, they were analyzed using a scanning electron microscope in a low‐vacuum mode with two different detectors. Results show a wide range not only in pigments but also in the methods used in their realizations. Moreover, the variety of pigments found allows distinguishability from different restorations carried out along centuries.