Enantioseparations of chiral compounds were studied in nonaqueous capillary electrochromatography (NAQ CEC) with cellulose and amylose tris(3,5-dimethylphenylcarbamates) (Chiralcel OD and Chiralpak AD, respectively) coated on the silica gels of various pore and particle size. Increasing intraparticle perfusive transport with increasing pore size of silica favorably affected peak efficiency and resolution of enantiomers, although some decrease of separation factor was observed in the pore size range 60-200 Angstrom. Further improvement of peak efficiency was observed when the particle size of silica was reduced from 5 to 3 mum. The effects of a separation medium and temperature are also reported and the data obtained in the same capillaries in CEC and capillary liquid chromatography (LC) mode are compared.