A highly dispersed ultramicro palladium-particle modified carbon fiber microdisk array electrode (Pd-CFE) was employed for capillary electrophoresis-elecrochemical (CEEC) detection of hydroxylamine (HA). The Pd particles obtained were in the nanometer scale, had a high electrocatalytic activity towards HA and exhibited good reproducibility and stability. A linear relationship between the current and the analyte concentration was found between 5 × 10−6and 1 × 10−3mol/1 of HA with a correlation coefficient of 0.9992. The detection limit was 5 × 10−8mol/1. The applicability of the method for the determination of HA in river water and waste water was investigated.