Non-destructive analysis of Venezuelan pottery samples of different sizes and shapes from various archeological sites along the Orinoco River in the middle of Venezuela was performed by radioisotope X-ray fluorescence. The method employed a low intensity 109Cd source. The precision of the measurements for Fe, Rb, Sr and Zr from three different areas on each side of one of the artifacts was about 5%. A comparison of the data analysis using gross peak intensities and net peak intensities employing a digital filter technique to eliminate the background is presented. Finally an attempt to discriminate the samples of one location from another one or ones, assuming that the potter's clays were from different sources, is described.