Thiamine is a primary catalyst of carbohydrate production from a simple chemical. As the best immobilization method, we succeeded in immobilization of thiamine on a cation exchange resin, and formaldehyde polymerization with the immobilized catalyst. The desorption and decomposition of the immobilized thiamine can be suppressed in an organic solvent and by using the action exchange resin in the sodium ion form. The main product is 1,3-dihydroxyacetone in all reaction under our conditions. The effect of the base concentration and the diffusion in the particle on the reaction rate are not observed under our conditions. Formaldehyde polymerization with the thiamine immobilized resin in 1,4-dioxane proved to be able to express the equation,-d [formaldehyde]/dt = k [thiamine] [formaldehyde]. The activation energy of the reaction can be estimated to be approximately 82 kJ mol(-1).