Products with a Protected Denomination of Origin (PDO) are vulnerable to misdescription of their true geographical origin. In this work a method has been developed that allows the authentication of La Vera paprika powder (Pimentón de la Vera), a PDO product from the central-west Spanish region, Extremadura. The mass fractions of Br, Ca, Cr, Cl, Cu, Fe, K, Mn, Ni, P, Rb, S, Sr and Zn determined by energy dispersive X-ray fluorescence (ED-XRF) are used for classification purposes by multivariate analysis using Soft Independent Modelling of Class Analogy (SIMCA) (PCA-Class) and Partial Least Square-Discriminant Analysis (PLS-DA). Sixty-seven paprika samples purchased in supermarkets around Europe and on-line via the official web-site of Pimentón de La Vera, were used to build up the models for prediction purposes. The PCA-class model of La Vera paprika powder had a sensitivity of 82%, a specificity of 100% and an accuracy of 91%, whereas the PLS-DA model had a sensitivity of 100%, a specificity of 91% and an accuracy of 96%.