A simple radioisotope x-ray fluorescence method for determining the relative mass fractions of rubidium, strontium and zirconium combined with principal component analysis was employed to investigate specimens of archaeological majolica ceramics tentatively assigned to the Puebla (Mexico) provenance by stylistic features. Principal component analysis with this x-ray fluorescence data could only separate the samples of one of the four groups from the other three as suggested from the thermoluminescence glow curves. Similarly, when the thermoluminescence data were analyzed by the principal component technique only the same group could be separated from the three others. However, the X-ray fluorescence method could confirm and separate the samples of the four groups with the additional information from the thermoluminescence data. Hence it can be concluded that the clay and/or temper materials from the different specimens of the four groups are different. The difference in the clay materials could be from contamination or different sources of the components of the clay paste themselves. It is concluded that the difference is due to the clay source, since samples found at the same locations belonged to more than one group.