The -2,3-bis(benzyl ether) of xylan, a natural polysaccharide, has been prepared by using a new benzylation method. This method was first tested on methyl-β-D-xylopyranoside, the monomer model of xylan. It implies the use of potassium hydroxyde, a crown ether as a catalyst, and benzyl bromide as a benzylating agent. Perbenzylated xylan is obtained with a good yield (80%) in a one-step reaction. It is soluble in most organic solvents. The 13C- and 1H-NMR spectra of this polymer were assigned and are typical of a regular linear polymer. Differential thermal analysis and thermogravimetry indicate the temperature range at which this polymer can be processed at high temperature.