To delineate the process of pancreatic stone formation, stones from four patients were studied with a scanning electron microscope and X-ray probe microanalyser. The stones consisted of a central core and surrounding shell. Two kinds of stones were demonstrated: one had a core composed of a calcium-rich amorphous substance and interlacing fibrils; the other had a core consisting of multiple cavities with smooth walls composed of a calcium-deficient amorphous substance. The shells showed a common structure: zones of layers or bands of a calcium-rich amorphous substance, network fibrils filled with a calcium-rich amorphous substance, and laminated parallelogrammic or polygonal plates of calcite parallel to the surface in one layer and oblique or perpendicular in the next layer. Calcium was in the crypto-crystalline state as well as crystalline state of calcite. Crystalline calcite showed spiral and epitaxial growth along with findings of dissolution, resembling cholesterol crystals of gall stones. Pancreatic stones are probably formed through central core formation and layered growth of a shell. Comparison of stones and protein plugs suggests that protein plugs can grow to stones with calcite deposition accompanied by precipitation of network fibrils and an amorphous substance.