Desulfated chondroitin sulfate C, a synthetic polysaccharide, was successfully developed as a novel chiral selector in capillary electrophoresis. It was first applied to the enantioseparation of the drugs of dihydropyridine class. The racemic mixture of cilnidipine, a new calcium channel antagonist for the treatment of hypertension, was resolved for the first time. The effects of buffer pH, concentration of the chiral additive and applied voltage on the chiral separation were investigated. The optimum conditions were pH 2.50, 30 g/L for additive concentration and 10 kV for applied voltage. Under the optimized conditions the enantiomers of cilnidipine were completely separated with a resolution factor of 2.01. The method is simple and rapid with high separation efficiency.