Novel fluorogenic Edman reagents, 7-N,N-dimethylaminosulphonyl-4-(2.1,3-benzoxadiazolyl)isothiocyanate (DBD-NCS) and 7-aminosulphonyl-4-(2,1,3-benzoxadiazolyl)isothiocyanate (ABD-NCS) having no fluorescence themselves were synthesized. The derivatives of amino acids with DBD-NCS fluoresce at 505 nm with excitation at 385 nm. They were separated on a reversed-phase HPI.C column and detected at the sub-picomol level. Ala-Phe derivatized with DBD-NCS was cleaved by acid to generate DBD-thiocarbamyl-Ala.