We have investigated the electronic states of clean Fe(001) and oxygen adsorbed Fe(001)–p(1 × 1)-O films epitaxially grown on MgO(001) substrates by means of polarization-dependent angle-resolved photoemission spectroscopy (ARPES) and extensive density-functional theory (DFT) calculations. The observed Fermi surfaces and band dispersions of pure Fe near the Fermi level were modified upon oxygen adsorption. By the detailed comparison of ARPES and DFT results of the oxygen adsorbed Fe surface, we have clarified the orbital-dependent p–d hybridization in the topmost and second Fe layers. Furthermore, the observed energy levels and Fermi wave numbers for the oxygen adsorbed Fe surface were deviated from the DFT calculations depending on the orbital characters and momentum directions, indicating an anisotropic interplay of the electron correlation and p–d hybridization effects in the surface region.