During recent years the surface electronic states of cobalt nanoislands grown on Cu(111) and Au(111) have been extensively studied and still yield fascinating results. Among magnetic surfaces, cobalt islands are particularly appealing because of their spin-polarized electronic states near the Fermi energy, involving localized d states of minority character, as well as free-like s–p states of majority character. We show here that these states are a sensitive probe to minute changes of structural details such as strain and stacking, and therefore constitute an ideal playground to study the interplay between structural and spin-related properties. Due to their size, cobalt islands on Cu(111) offer the additional opportunity to host single-magnetic adsorbates suitable for spin-polarized scanning tunneling microscopy and spectroscopy (SP-STM and SP-STS). We establish here that, in an energy interval just below the Fermi level, the spin-polarization of a transition-metal atom is governed by surface-induced states opposite in sign compared to the island, while the spin-polarization of Co-Phthalocyanine molecules is governed by molecular states. This opens up interesting perspectives for controlling and engineering spin-polarized phenomena at the nanoscale.