Oxygen dissociation and activation on surfaces play a crucial role in heterogeneous catalysis and oxidation processes. In this study, we have conducted a series of scanning tunneling microscopy (STM) experiments combined with density functional theory calculation to investigate the oxidation process in a single crystal Co(0001) surface. For the first time, we show a comprehensive in situ STM study of the oxidation process of Co(0001) from an atomic point of view. With low O2 exposure at 90 K, chemisorbed oxygen pairs are observed showing a dumbbell-like STM feature. At a relatively higher temperature range of 160-250 K, a large-scale p(2 × 2)-O adlayer forms and the O adatoms show surprisingly high mobility. With the temperature of Co(0001) kept at ≥300 K, adsorption of oxygen leads to fast oxidation of the surface to amorphous cotton-like protrusions, which occur initially at the step/edge sites and interstitial defect sites.