Abstract: 8 nm Co nanoparticles with various crystalline structures called polymorphs were produced using different synthetic procedures, such as using reverse micelles, the thermal decomposition of organometallics approach or the hot injection process. These 8 nm Co nanoparticles differing by their crystalline structures are exposed to oxygen at elevated temperature. The fcc Co polycrystalline nanoparticles produce either Co-CoO yolk-shell or CoO hollow structures whereas amorphous Co nanoparticles produce Co-CoO core-shell nanoparticles. Furthermore, single domains with either hcp or ε crystalline structure behave differently upon oxygen diffusion. Co-CoO nanoparticles were produced from the hcp phase while CoO hollow nanoparticles were the product for ε-phase Co nanocrystals.