Understanding oxygen adsorption and dissociation on the five-fold coordinated titanium (Ti5c) site of the rutile TiO2 surface is important in clarifying chemical reaction processes. Accordingly, three different configurations of molecularly adsorbed O2, including parallel side-on, inclined side-on and end-on configurations, and their dissociation were directly observed with atomic resolution at 78 K by atomic force microscopy. Our results experimentally demonstrated that the three adsorbed O2 configurations could be changed by electric field stimulation. The initial configurations of the adsorbed O2 and transition of O2 configurations were related to their coverage. On the other hand, the tunneling current stimulation could dissociate these O2 species, indicating that they are precursors for the O adatom (Oad). It is proposed that the effect of electric field stimulation contributes to the transition of these three adsorbed O2 configurations, and the effect of the tunneling current is the main factor for the dissociation of the adsorbed O2. In addition, based on the atomic contrast and height histograms of Oad, different charge states of Oad were observed, which could coexist on the surface region. The present study demonstrates an intuitional observation of O2 adsorption and dissociation on the Ti5c site, and thus is expected to be useful to understand the surface reactions on the oxide surface.