The effect of the rare sugar D-psicose on chitosan production by Rhizopus oryzae was studied. The fungus was not able to utilize D-psicose as a sole source of carbon, either for germination of the spores or for growth of the vegetative cells. In a medium containing a low amount of D-glucose, however, D-psicose supplementation between 5 and 12 g/l caused enhancement of the productivity of chitinous substances, especially chitosan, in the cell walls. Substantial changes in the chitosan molecule were not observed from FT-IR or H-1 NMR data. It was inferred that a percentage of the D-psicose added was transformed into another rare sugar tentatively identified as D-tagatose. It was concluded that D-psicose activates the synthesis of chitosan in the cell walls probably through its transformation into another sugar such as D-tagatose.