Polysaccharide derivatives, such as phenylcarbamates and benzoates of cellulose and amylose, are known to show high chiral recognition abilities for many racemates when used as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). This type of CSPs has usually been prepared by coating the polysaccharide derivatives onto a macroporous silica gel without a chemical bond. Therefore, rather limited numbers of solvents can be used as eluents, and solvents, such as chloroform and tetrahydrofuran (THF), which swell or dissolve the polysaccharide derivatives cannot be used. The selection of a suitable eluent is very important for both analytical and preparative separations. In order to enhance the versatility of the polysaccharide derivative-based CSPs, the derivatives have to be immobilized. Here we review the immobilization methods of the polysaccharide derivatives mainly onto silica gel.