The wide distribution of the ester phosphorus is observed in starches from various sources. Potato starch is known to contain esterified phosphoryl group in its components.1,2) Takeda and Hizukuri have reported that the phosphate groups were located mostly in the B chain of amylopectin, whereas the phosphorylation of amylose was very little.3) Potato amylopectin contains 100 1000 ppm of the ester phosphorus.2) Furthermore, approximately 60% to 70% of the phosphate groups were linked to C 6 of the glucosyl residues, the almost all the rest being linked to C 3 and a very small part possibly being linked to C 2 of the glucosyl residues.2) Our attention was focused on the utilization of esterified phosphoryl group in potato starch, and succeeded to prepare new phosphoryl oligosaccharides (POs) from the starch hydrolysate. 4) In this article, we introduce our recent achievements in a new function of the oligosaccharides focusing on the application for soluble calcium and effect of remineralization on enamel lesion. In first, we tried to investigate a new functional food ingredient as soluble calcium. It is generally recognized that the absorbability of calcium is substantially dependent on its solubility in an aqueous solution, 5 7) because calcium will be absorbed in its free or ionized form in the intestine. 8,9) The adult human body contains about 1 1.2 kg of calcium, which amounts to about 1.5 2% of body weight. Of this, 99% is found in mineralized tissues, such as bones and teeth, where it is present as calcium phosphate (together with a small component of calcium carbonate), providing rigidity and structure.10,11) The remaining 1%, found in blood, extracellular fluid, muscle, and other tissues, play an important role in mediating vascular contraction and vasodilation, muscle contraction, Abstract: Phosphate ester groups are known to link to some glucosyl residues in starch molecule. We focused on the utilization of esterified phosphoryl group in potato starch components. In starch processing, the actions of the amylolytic enzymes were hindered by the phosphoryl groups linked to the glucosyl residue, and phosphoryl oligosaccharides (POs) were obtained as indigestible components by the enzymes. The POs were composed of two fractions, PO-1 and PO-2. Fraction PO-1 was the main fraction, and it was composed of maltotriose, maltotetraose and maltopentaose to which one phosphoryl group was attached. Fraction PO-2 was predominantly composed of maltopentaose and maltohexaose to which at least two phosphoryl groups were attached. The POs had the ability to form a soluble complex with calcium and had inhibitory effect on the formation of a calcium-phosphate precipitate. Based on the function of the POs, described above, we applied the POs of calcium (POs-Ca û R ) as a food ingredient. The POs-Ca was an advantageous food ingredient as a soluble calcium source. Relating to prevent of dental caries, POs can not be fermented by cariogenic microorganisms, mutans streptococci, and reduces the plaque pH fall in vitro. Moreover, ...