Synchrotron-based XANES characterization of sulphated sulphur combined with atomic force microscopy and transmission electron microscopy (imaging and diffraction) allow insights into the crystallization of the calcareous units produced by invertebrates. As a result of a series of converging data, reticulate crystallization of the amorphous Ca-carbonate molecules conveyed to the micron-thick growth layer by the sumicrometric organo-mineral units seems a reasonable hypothesis, providing us with a method of explaining the multiple and taxonomy-linked ‘vital effects’ which have long been recognized among the calcareous biocrystals.