Sialolithiasis refers to pathological minerilazation in the salivary glands and ducts. Aiming to a better understanding of the formation phenomena, structural and morphological analysis of a relatively large ensemble of sialoliths extracted from 22 patients via sielendoscopy was performed. Characterization methods, including Fourier Transform Infrared (FTIR) Spectroscopy, X‐Ray Diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM), showed that the large majority of 90% of sialoliths were composed of carbonate apatite as the inorganic phase, while SEM imaging revealed the presence of bacteria in 13 cases. Furthermore, carbonate apatite crystals in the form of parallel or randomly oriented sheets were observed and in some cases rhombohedral calcite‐type nanocrystals were detected. The present findings may contribute to a better understanding of the formation mechanisms in vivo and and contribute to the treatment of sialolithiasis.