Hydration behavior of a rare sugar, D-psicose, was investigated based on measurements of the dielectric relaxation and the water activity in its aqueous solutions. Dielectric relaxation spectra in the frequency domain were obtained from time domain reflectometry. The dielectric relaxation time was then determined by fitting the spectra to a Cole-Cole type equation and used to evaluate the average hydration number representing the average number of water molecules forming a complex with a sugar molecule at infinite dilution. The concentration dependence of the dielectric relaxation time in aqueous solutions of all examined sugars generated a single master cur ve. The average hydration number of psicose was found to be identical with that of fructose. Only slight differences were noticeable among the concentration dependences of the water activity of monosaccharides. The equilibrium constant of hydration of sugar was calculated by considering material balances in an aqueous solution of sugar and using experimentally obtained values of the average hydration number and the water activity. The equilibrium constant values increased in the order of glucose < fructose � psicose < trehalose < sucrose < maltose. The present results suggest that both fructose and psicose interact with water in a similar manner.