Solid-solid reaction, particularly in the Fe-O binary system, has been extensively studied in the past decades because of its various applications in chemistry and materials and earth sciences. The recently synthesized pyrite-FeO2 at high pressure suggested a novel oxygen-rich stoichiometry that extends the achievable O-Fe ratio in iron oxides by 33%. Although FeO2 was synthesized from Fe2O3 and O-2, the underlying solid reaction mechanism remains unclear. Herein, combining in situ X-ray diffraction experiments and first-principles calculations, we identified that two competing phase transitions starting from Fe2O3: (1) without O-2, perovskite-Fe2O3 transits to the post-perovskite structure above 50 GPa; (2) if free oxygen is present, O diffuses into the perovskite-type lattice of Fe2O3 leading to the pyritetype FeO2 phase. We found the O-O bonds in FeO2 are formed by the insertion of oxygen into the Pv lattice via the external stress and such O-O bonding is only kinetically stable under high pressure. This may provide a general mechanism of adding extra oxygen to previous known O saturated oxides to produce unconventional stoichiometries. Our results also shed light on how O is enriched in mantle minerals under pressure.