We introduced colominic acid as a new chiral selector for capillary electrophoresis of basic drugs. Use of a low concentration phosphate buffer containing this polysaccharide and a Polybrene/colominic acid double coated capillary allowed excellent separation of the enantiomers of primaquine, chloroquine and tryptophan. Other drugs giving partial enantioseparation include laudanosine and salbutamol. Capillary coating with Polybrene followed by colominic acid eliminated the problems of peak tailing and low reproducibility of migration time in uncoated capillaries. The optimum pH was in the acidic region but varied among drugs. A low capillary temperature of 16 degrees C and a colominic acid concentration of 9 w/v% are recommended for practical analysis of these drugs. Colominic acid preparations having higher molecular masses gave better enantioseparation, and N-acetylneuraminic acid, the component monosaccharide, did not give any enantioseparation.