The artworks of the Archdiocesan Museum of Sacred Art of Rio de Janeiro (MAAS‐RJ) are distinguished for their combination of Luso‐Brazilian Sacred Arts and dedication to historical heritage preservation. An in situ analysis using x‐ray fluorescence (XRF) was conducted on five pieces from the collection, including Our Lady of the Expectation, Our Lady of Lapa, Our Lady of Penha de France, Saint Sebastian, and the Glory of the Divine. The analysis employed the portable Bruker Tracer‐III‐SD equipment, which features a Rhodium‐target x‐ray tube and a Silicon detector. Spectra were obtained with the device set at 40 kV and 35 μA, with a 60‐s exposure time. The multi‐element analysis identified the elements present in the pictorial layers, allowing the identification of pigments used in the original polychromes and repaints. The data revealed a diverse composition of pigments across the original, repainted, and polychrome regions. Elements indicative of pigments applied after the creation of the works, consistent with restoration and interventions, were detected. The XRF analysis confirmed the use of gilding techniques in some sculptures, such as Our Lady of the Expectation and the Glory of the Divine. The sculpture of Our Lady of Penha de France exhibited gilding techniques with sgraffito. This study provided the elemental composition of the examined sacred artworks, suggesting potential pigments regardless of their preservation conditions.