Pressure is well-known to significantly change the bonding patterns of materials and lift the reactivity of elements, leading to the synthesis of unconventional compounds with fascinating properties. Titanium-oxygen (Ti-O) compounds (e.g., TiO2) are attracting increasing attention due to their attractive electronic properties and extensive industrial applications (e.g., photocatalysis and solar cells). Using the effective CALYPSO structure searching method combined with first-principles calculations, we theoretically explored various oxygen-rich Ti-O compounds at pressures ranging from 0 to 200 GPa. Our results revealed, unexpectedly, that pressure stabilizes two hitherto unknown stoichiometric oxygen-rich Ti2O5 and TiO3 compounds. Ti2O5 crystallized in P-421 c structure, whose remarkable feature is that it contains a peroxide group (O22-) with an O-O distance of 1.38 Å at 150 GPa. The trioxide TiO3 is an ionic metal and is the oxygen-richest compound known thus far in the Ti-O system. It adopts a high symmetry (space group Pm-3 n) structure consisting of a 12-fold coordinated face-sharing TiO12 icosahedron, where Ti has the highest coordination number with O among all Ti-O structures. The underlying mechanisms for the stabilization of Ti2O5 and TiO3 lie in the higher coordination number and denser structure packing. Our current results unravel the unusual oxygen-rich stoichiometry of Ti-O compounds and provide further insight into the diverse electronic properties of Ti oxides under high pressure.