The electron transfer from aniline and its N-methyl as well as N-phenyl substituted derivatives (N-methylaniline, N,N-dimethylaniline, diphenylamine, triphenylamine) to parent solvent radical cations was studied by electron pulse radiolysis in n-butyl chloride solution. The ionization results in the case of aniline (ArNH2) and the secondary aromatic amines (Ar2NH, Ar(Me)NH) in the synchronous and direct formation of amine radical cations, as well as aminyl radicals, in comparable amounts. Subsequently, ArNH2center dot+ deprotonates in a delayed reaction with the present nucleophile Cl-, and forms further ArNHcenter dot. In contrast, tertiary aromatic amines such as triphenylamine and dimethylaniline yield primarily the corresponding amine radical cations Ar3Ncenter dot+ or Ar(Me-2)Ncenter dot+, only. The persistent Ar3Ncenter dot+ forms a charge transfer complex (dimer) with the parent amine molecule, whereas Ar(Me-2)Ncenter dot+ deprotonates to carbon-centered radicals Ar(Me)NCH2center dot.