Fourier transform Raman (FT-Raman) spectroscopy and Fourier transform infrared spectroscopy (FT-IR) were used as the main analytical techniques for the determination of human gallstone structural composition. These techniques provide rapid, qualitative and quantitative information about stone structure. The gallstones were obtained from. 40 patients during both surgical operations and laparoscopy. The results of FT-Raman and FT-IR analysis allowed to distinguish of four main groups of gallstones according their cholesterol and bilirubinate salt content. Our studies were extended to trace element analysis by means of proton induced X-ray emission (PIXE). On 14 elements detected, six elements Ca, Mn, Fe, Cu, Zn and Br were chosen for quantitative analysis. The concentration levels of these elements varied depending the chemical structure of the gallstones. The relationship between Ca and Cu appears to be of particular significance. In this paper a correlation between stone structure and trace element concentrations is presented.