Abstract We have measured the spin-resolved 3 p and 3 s core-level photoemission as well as M 23 VV Auger electron spectra of ferromagnetic Ni. The observed core level spin polarization spectra can be interpreted in terms of the multiplet structures based on the impurity Anderson model. In the non-resonant normal M 23 VV Auger-electron spectrum, positive spin polarization is clearly found not only for the “3 d 8” final state but also for the state with the kinetic energy beyond 62eV (binding energy of the Ni 3 p core level minus the work function). The positive spin polarization of the “3 d 8” main structure is understood as the final state mixing of the 3 d 7 and 3 d 8 states in contrast to the previous interpretation. The positive spin polarization above 62eV is ascribed for the first time to the secondary electron excitation.