A capillary electrophoresis with electrochemical detection was developed for the simultaneous determination of three flavonoids (naringenin, rutin, quercetin) and ascorbic acid. It was found that naringenin, rutin, quercetin and ascorbic acid were well separated within 5 min in borate buffer solution (pH 8.6, 24 mM). The detection limit was 1.0 microM for naringenin, 8.0 microM for rutin, 2.0 microM for ascorbic acid and 0.5 microM for quercetin. The protocol was successfully applied for the determination of the analytes in rat serum and excrement. Recovery results ranged from 90.9 to 108.6%.