We investigate the electronic structure and noncovalent interactions within cationradical complexes that are relevant in the electron impact mass spectrometry of N-(2-furylmethyl)anilines, 4-RC6H4-NH-CH2-C4H3O with (R = -H, -OCH3, -CH3, -F, -Cl, -Br). In particular, we consider the reactive intermediates that precede the final products of two previously suggested dissociation pathways for these systems, i.e., (i) a direct cleavage of the NH-CH2 bond and (ii) an isomerization/fragmentation mechanism. The study is performed by means of correlated calculations (UCCSD and UMP2) together with density functionals (UM06 an UM06-2x) along with the triple-zeta quality basis set 6-311++G(2d,2p). In addition, we carried out a topological analysis of the electron density in accordance with the quantum theory of atoms in molecules (QTAIM) together with the examination of the noncovalent interaction (NCI) index. In contrast with previous studies based on the UB3LYP approximation, we could determine the transition states associated with both fragmentation pathways. The RiceRamspergerKasselMarcus theory, used to determine the relative importance of these dissociation mechanisms, indicates that whereas the direct cleavage and the isomerization/fragmentation reaction routes have similar constant rates at low energy, the former prevails when the energy of the system is increased. The QTAIM analysis reveals that the charge of the cationradical complex is mainly located on either a furfuryl (direct cleavage mechanism) or a pyrylium (isomerization/fragmentation pathway) ion and that these units interact with a neutral radical aniline moiety. The localization of the positive charge in either a furfuryl or pyrylium cation is in agreement with the preminecence of the m/z = 81 fragment in the mass spectrometry of N-(2-furylmethyl)anilines. Moreover, the QTAIM properties indicate that the a unpaired electron of the system is principally distributed over the nitrogen and the ortho and para carbon atoms with respect to the -NH group in the R-C6H4-NH unit. The investigation of the NCI index and the intermolecular bond critical points and bond paths gives an account of the NCIs linking the radical cation clusters under consideration. Finally, we found correlations which indicate that the concentration of the m/z = 81 fragment in a mass spectrum is reduced with the interaction energy of the radical complex from which it is originated. Altogether, this work shows how the combination of suitable electronic structure calculations along with post wave function analyses can yield important insights about the formation and properties of cationradical complexes relevant in mass spectrometry.