Auger-photoelectron coincidence spectroscopy (APECS) has been used to examine the electron correlation and itinerance effects in transition metals Cu, Ni and Co. It is shown that the LVV Auger, in coincidence with 2p photoelectrons, spectra can be represented using atomic multiplet positions if the 3d-shell is localized (atomic-like) and with a self-convoluted valence band for band-like (itinerant) materials as explained using the Cini-Sawatzky model. For transition metals, the 3d band changes from band-like to localized with increasing atomic number, with the possibility of a mixed behavior. Our result shows that the LVV spectra of Cu can be represented by atomic multiplet calculations, those of Co resemble the self-convolution of the valence band and those of Ni are a mixture of both, consistent with the Cini-Sawatzky model.