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A new convenient method has been developed for the synthesis of well-defined aniline oligomers containing 3 to 8 aromatic amine units with amino or aryl end-groups. The method consists of a single-step reaction of the aromatic amines having at least one amino end-group with other aromatic amines in an acidic medium with or without external oxidizing agents. The oxidation state of the oligomers can be changed via simple redox reactions. A possible mechanism for the reaction involves an electrophilic aromatic substitution of nitrenium cation to aromatic amines.