Disclosed is a process for producing a crystalline sugar comprising D-psicose and D-allose. Also disclosed is a process for producing the sugar. A complex crystalline sugar comprising D-psicose and D-allose. The compositional ratio between D-psicose and D-allose in the sugar is about 1:1 to 1:4. A process for producing a complex crystalline sugar comprising D-psicose and D-allose, the process comprising producing a complex crystalline sugar comprising D-psicose and D-allose from a sugar solution containing D-psicose and p-allose and collecting the complex crystalline sugar. The solvent of the sugar solution used in the production of the complex crystalline sugar is water or a mixture of water and ethanol. The sugar solution containing D-psicose and D-allose is produced by a process comprising reacting D-psicose with L-rhamnose isomerase to convert D-psicose into D-allose. The L-rhamnose isomerase is derived from a strain (IPOD FERM BP-08593) belonging to Pseudomonas stutzeri.