An improved method for the concurrent determination and separation of cations and anions by microchip electrophoresis with capacitively coupled contactless conductivity detection (ME-(CD)-D-4) is described. Two kinds of microchip structures were designed. The first microchip has a long bent separation channel. And for the defects of the first microchip, the second microchip with a Y-type separation channel has been proposed. The background electrolyte (BGE) composed of 20mm His/MES and 0.01mm CTAB was optimized for inhibiting the electroosmotic flow (EOF). Due to the low electroosmotic flow, the cations and anions migrate in opposite directions and can be separated from each other. With the precisely controlled high-voltage, cations and anions can be migrated in microchannels according to our requirements and sequentially detected by a (CD)-D-4 detector built in-house. Samples containing K+, Na+, Li+, Cl-, F- and PO43- were analyzed simultaneously in a single run (within 140 s) by both methods. The reproducibility obtained by both methods remained below 5% for migration time and within 3.5-9.1% for peak areas. The proposed concurrent determination methods are inexpensive, simple, fast, ease of operation, high degree of integration.