The end-on oxygen-bound sulfur monoxide (SO) complex of titanium oxyfluoride [OTiF2(eta(1)-OS)] was prepared via the isomerization of a bidentate sulfur dioxide complex of titanium difluoride [TiF2(O2S)] under UV-vis irradiation in cryogenic matrixes. IR spectroscopy in combination with O-1(8) and S-34 isotopic substitutions and density functional theory calculations were employed to identify the product structures and reaction mechanisms. According to the experimental and theoretical results, the OTiF2(eta(1)-OS) complex was characterized to possess a triplet ground state, with the oxygen-bound SO ligand being similar in character to the neutral diatomic SO molecule. It is more stable than the sulfur-bound OTiF2(eta(1)-SO) isomers by about 15.0 kcal/mol but less stable than the TiF2(O2S) precursor by 14.4 kcal/mol at the B3LYP level. The formation of OTiF2(eta(1)-OS) involves cleavage of the 5-0 bond of TiF2(O2S) with an energy barrier of 25.6 kcal/mol.