The biofuel chemicals, 5-ethoxymethylfufural (EMF) and 5-methoxymethylfufural (MMF) have been prepared from various carbohydrates in alcoholic solvents. The porous polymeric material PSDVB-SO3H was employed as a heterogeneous catalyst in this investigation and the reaction parameters; time, temperature, catalyst/feedstock loading and co-solvent were optimized. As a result of the acid density and mesoporous structure, PSDVB-SO3H efficiently catalyzed the ethanolysis of fructose to EMF in a 67.5% yield (2 h, 393 K). Whereas MMF was obtained in a 31.6% yield from the catalytic methanolysis of fructose. Compared to commercial Amberlyst-15, less time was required for PSDVB-SO3H to obtain a comparable yield of EMF. Alkyl levulinates and 5-hydroxymethylfurfural (HMF) were the main co-products in these reactions, with yields in the range of 0-67% obtained from the catalytic alcoholysis of fructose. Furthermore, by using a "two-step, one-pot" route with successive addition of zeolite zeolite and PSDVB-SO3H to a solution of glucose, EMF was achieved in a yield of 39.4%.