AbstractThe pigments used in four of the most representative paintings of the Brazilian artist Rodolfo Amoedo were characterized by means of the EDXRF technique. The analyzed paintings were ‘The Last Tamoyo’ (1883), ‘Study of a Woman’ (1884), ‘Bust of Mrs. Amoedo’ (1892) and ‘Bad News’ (1895). EDXRF measurements were carried out with a portable system developed by the Nuclear Instrumentation Laboratory, consisting of an x‐ray tube Oxford TF3005 with a W anode, operating at 25 kV and 100 µA, and a Si‐PIN XR‐100CR detector from Amptek. Several spectra were obtained in each color and distinct hue of the paint layer, with an acquisition time of 300 s and a beam collimation of 2 mm. Some pigments used by the artist were zinc white, lead white, ochre, umber, vermilion, Prussian blue, cobalt blue, cadmium yellow, black iron oxide and manganese violet. In the painting ‘The Last Tamoyo’, titanium white was identified in some alteration areas, which were restored during the twentieth century. These results—together with computed radiography analyses—will be used to create a database about the nineteenth‐century collection of the National Museum of Fine Arts, in order to assist restorers, conservators, art students and researchers in the field of archeometry. Copyright © 2009 John Wiley & Sons, Ltd.