The behavior of water-soluble p-sulfonic calix[4]arene in capillary electrophoresiswas first reported. A mixture of nitrophenol isomers was completely separated using only3 mmol/L calixarene. The efficiency of 3. 0 × 105 plates/m was achieved and the detectionlimits were 33. 6, 21. 8 and 16. 2 pg for o-, m- and p- nitrophenol respectively under thecon-ditions fused-silica capillary(44 cm ×50 μm i. d., effective length 37 cm), phosphate buffer(50 mmol/L, PH 5. 0), 25℃, 14 kV, 275 nm and 1 s vacuum load.