An ion-exclusion chromatography method with ion-exchange enhancement of conductivity was developed for the selective separation and sensitive determination of hydrazine ion from alkali/alkaline earth metal cations and ammonium ion. Hydrazine ion was separated by ion-exclusion/penetration effect from other cations on a weakly basic anion-exchange column in the OH - form (TSKgel DEAE-5PW). Moreover, two different ion-exchange resin columns were inserted between the separating column and conductimetric detector in order to improve the sensitivity of hydrazine ion. The first enhancement column packed with a strongly basic anion-exchange resin in the SO 4 2 - form (TSKgel SAX) for hydrazine ion can convert from N 2 H 5 OH to (N 2 H 5 ) 2 SO 4 . Moreover, the second enhancement column packed with a strongly acidic cation-change resin in the H + form (TSKgel SCX) can convert to H 2 SO 4 . As a result, the sensitivity of hydrazine ion using two conductivity enhancement columns could be 26.8-times greater than using the separating column alone. This method was effectiveness also for the enhancement of ammonium ion (6.1-times) and sodium ion (1.2-times). The calibration graph of hydrazine ion detected as H 2 SO 4 was linear over the concentration range of 0.001-100ppm (r 2 =0.9988). The detection limit of hydrazine ion in this system was 0.64ppb. Therefore, hydrazine ion in real boiler water sample could be accurately determined, avoiding the interference of other cations.