An HPLC post column chemical derivatization procedure based on the interaction between an acridinium triflate and amines to form highly colored derivatives on-line is described for the determination of aromatic amines. Benzocaine and butesin, local anesthetic agents that contain the aromatic amine group, were used as model compounds. Reversed-phase HPLC conditions were developed for both the separation of analytes and the reaction between analytes and the acridinium triflate in the system. Three-dimensional knitted teflon shape coils and the internal diameter and length of the coils were important parameters in reducing band broadening and background noise. N-Methyl-9-chloroacridinium triflate was shown to be applicable to the determination of primary aromatic amines, selected secondary aromatic amines, hydrazides, and hydrazines. Application of the on-line chemical derivatization procedure to the analysis of pharmaceutical dosage forms containing procainamide (primary aromatic amine), isoniazid (hydrazide), and hydralazine (hydrazine) is also described.