This report presents the preparation and characterization of two interconvertible titanium ozonide complexes using matrix-isolation infrared spectroscopy and density functional theory calculations (B3LYP/6-311+G(d)). The titanium atoms react with O-2 to form primarily the inserted TiO2 molecules in solid argon, which further react with O-2 to form OTi(eta(2)-O-2)(eta(2)-O-3) via a weakly bonded TiO2(O-2)(2) intermediate. The OTi(eta(2)-O-2)(eta(2)-O-3) complex is characterized as [(TiO)(2+)(O-2(-))(O-3(-))], that is, a side-on-bonded oxo-superoxo titanium ozonide complex. The side-on-bonded complex rearranges to a less stable end-on-bonded OTi(eta(2)-O-2)(eta(1)-O-3) isomer under 532 nm laser irradiation, while the reverse reaction (end-on to side-on) proceeds upon sample annealing.