The molecular orientation and structure of vacuum deposited (VD) films of titanyl phthalocyanine (TiOPc) were revealed by X-ray diffraction (XRD) and electron paramagnetic resonance (EPR). The XRD pattern of the VD film of TiOPc shows a diffraction peak yielding the plane separation of 14 Å. The EPR spectra indicate that the molecular orientation strongly depends upon the deposition time. Thermal annealing at 45^oC for two hours induced an orientation change in the TiOPc films where molecule aligns perpendicular to the substrate surface. However, shorter or longer thermal process for one or three hours resulted in the formation of amorphous structure. The XRD patterns of the powder and thin film of TiOPc suggest that TiOPc is oriented perpendicular to the glass substrate. Angular variation in the linewidth of EPR spectra shows a two-dimensional spin-chain in the VD films, indicating a planer network for the spin-chain interaction. Annealing of the VD films promotes molecular reorientation in the film.