Rare sugars are monosaccharides with tremendous potential for applications in pharmaceutical, cosmetics, nutraceutical, and flavors industries. The four rare sugars, including; gulose, allose, altrose and talose are stereoisomers that are different in the hydroxyl group orientation (axial or equatorial) on the C2-4 atoms. The DFT, AIM, and, NBO calculations were used to probe the probability of formation of internal H-bonds in four rare sugars. The AIM analysis identified that altrose and talose can form three predominantly intramolecular H-bonds, whereas gulose and allose revealed one and two H-bonds, respectively and these normal intramolecular H-bonds are mostly closed-shell interactions. The theoretical calculated O-H stretching FT-IR vibrational frequencies confirmed that the intramolecular H-bonds shifted toward low frequencies in comparison to the free hydroxyl group, which caused the red-shift. Also, the lowest IR frequency in each sugar was related to the structure with the highest stabilization energy and the most strongest intramolecular H-bonds.