CE with tris(2,2'-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection for the quantitative determination of isocyanates was first reported. Hexamethylene diisocyanate (HDI) and hexyl isocyanate (HI) were used as the model analytes. Commercially available N,N-diethyl-N'-methylethylenediamine was used as the derivatization reagent. It has both a secondary amine group and a tertiary amine group. The secondary amine group can quantitatively react with isocyanate group, and the tertiary amine group can react with Ru(bpy)(3)(2+) to produce strong ECL signal for sensitive detection. The derivatization reaction was almost instantaneous and is much faster than other reported derivative reactions using other derivative reagents. The urea formed was stable. Linear calibration curve was obtained in the range from 0.01 to 10 mu M for HDI, and 0.02 to 20 mu M for hexyl isocyanate (HI). The detection limit is 0.01 mu M for HDI and 0.02 mu M for HI. The method is more sensitive than UV-detection and electrochemical detection. For practical application, recovery higher than 90% for HDI and HI was