The chemical behaviour of oxotitanium(rv) phthalocyanine (OTiPc) in mixtures of dichloromethane and trihalogenoacetic acids was studied by means of spectroscopic measurements. In dichloromethane-trifluoroacetic acid mixtures, OTiPc was relatively unstable, undergoing gradual decomposition via the radical cation of OTiPc; phthalimide and 3-iminoisoindolin-1-one were isolated. In dichloromethane-trichloroacetic acid mixed solvent, on the other hand, a stable solution of OTiPc was obtained with no formation of the radical cation. A monolayer of OTiPc was formed upon spreading this solution onto the water surface and was deposited on substrates with a horizontal lifting method to form a multilayer film. Polarized visible and near-IR absorption spectra and X-ray diffraction of the film indicated a specific order of molecular orientation.