We recently developed an approach for calculation of the electron–phonon (electron–ion in a more general case) coupling in materials based on tight-binding molecular dynamics simulations. In the present work, we utilize this approach to study partial contributions of inter- and intraband electron scattering events into total electron–phonon coupling in Al, Au, and Cu elemental metals and in AlCu alloy. We demonstrate that the interband scattering plays an important role in the electron–ion energy exchange process in Al and AlCu, whereas intraband d–d transitions are dominant in Au and Cu. Moreover, inter- and intraband transitions exhibit qualitatively different dependencies on the electron temperature. Our findings should be taken into account for the interpretation of experimental results on the electron–phonon coupling parameter.