During the course of our studies, we found the relationship between the fluorescence characteristics (the fluorescence intensity and the maximum excitation and emission wavelengths) of benzofurazan compounds and the sum and difference of Hammett substituent constants (σp) at the 4- and 7- positions. This prompted us to design a useful fluorogenic derivatization reagent having the benzofurazan skeleton for alcohols along this line of thought. Accordingly, the fluorogenic derivatization reagents, which have no fluorescence themselves, 7-N,N-dimethylaminosulfonyl-4-(2,1,3-benzoxadiazolyl) isocyanate (DBD-NCO), 7-phenylsulfonyl-4-(2,1,3-benzoxadiazolyl) isocyanate (PSBD-NCO), and 7-methylsulfonyl-4-(2,1,3-benzoxadiazolyl) isocyanate (MSBD-NCO), were synthesized. Among the derivatives derived from the three reagents, that from PSBD-NCO was most strongly fluorescent. PSBD-NCO reacted with 1-octanol within 4 h in acetonitrile solution in the absence of a catalyst at 60 °C. The derivatives with four alcohols (1-octanol, 1-nonanol, 1-decanol, and 1-undecanol) were separated on a reversed-phase column and detected fluorimetrically at 490 nm with the excitation at 368 nm. The detection limits were at the 10-femtomole level. PSBD-NCO was superior to other fluorescent-labeling reagents with regard to the avoidance of the interfering peaks derived from the reagents themselves and degradation products in the chromatogram. The effectiveness of our approach is disccussed in terms of the development of new fluorogenic reagents.