The typical FCC Al and Cu with distinct electronic configurations performing the difference in oxidation behaviors are our focus. The optimized reconstruction, thermodynamical energies, electronic properties, and diffusion dynamics of Al(111) and Cu(111) adsorption and penetration systems with on-surface O coverages from 0.25 ∼ 1 ML have been studied using DFT methods. The qualitatively different binding behaviors of O-Al/Cu(111) adsorption systems as the increasing coverage can be illustrated systemically by the relaxations of outermost layers, electron transfer, and orbital hybridization. Based on this benchwork, it can be seen that the initial O-penetrating configurations are energetically less favorable and present more significant surface reconstructions mainly due to the strong interactions between on-surface and sub-surface oxygen in the crystal lattice. A metal pulled-off effect with a larger missing-row stepped on-surface reconstruction only in Cu can be observed over the whole pre-coverage in the existence of sub-surface O, mainly due to the significant strain-induced interactions dominate in the Cu lattice. This reconstruction will suggest the possible formation of a larger channel to further oxidize the inner Cu atoms. On-surface/sub-surface O species play a cooperative role in surface reconstruction and stability of Al/Cu(111) and enlighten us on the distinct atomic-level mechanisms of the initial oxidation process.