The ultrastructure of the inner dental epithelial cells (IDE) and odontoblasts in elasmobranch (Raja erinacae) tooth buds was investigated by transmission electron microscopy to determine what contribution each cell type makes to the forming enameloid matrix. Row II, early stage, IDE cells contained few organelles associated with protein synthesis, whereas preodontoblasts appeared competent to initiate extracellular matrix production. Row III IDE cells are also devoid of organelles related to secretory protein synthesis, although these IDE cells accumulated large pools of intracellular glycogen. The glycogen appeared to be packaged into vesicles and exocytosed into the lateral extracellular space toward the forming enameloid matrix. Row III odontoblasts had a morphology consistent with an active protein secretory cell. No procollagen granules were present within the odontoblasts, however, nor were many collagen fibers observed in the enameloid matrix. Instead, non-collagenous "giant" fibers having 17.5-nm periodic cross striations were associated with the invaginations of odontoblast cell processes. Giant fibers, which spanned a clear zone adjacent to the odontoblasts, terminated within the enameloid matrix. Smaller 25-nm-wide "unit" fibers emanated from the giant fiber tips to form the bulk of the enameloid matrix. The clear zone, which separated the odontoblasts from the enameloid matrix at early stages, diminished in size at later stages until the odontoblast processes were completely embedded in the enameloid matrix. Nascent enameloid crystallites were observed only after a layer of unmineralized predentin was deposited beneath fully formed enameloid matrix. The results suggest that the major constituent of the enameloid matrix in skates is a non-collagenous protein derived from the odontoblasts. The inner dental epithelial cells appear to contribute large quantities of carbohydrates to the forming enameloid matrix.