Structure and spin-chain interaction of vacuum-deposited films of titanyl phthalocyanine (TiOPc) was revealed by X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. The XRD pattern of the TiOPc vacuum-deposited films showed a diffraction peak with a plane separation of 14 Angstrom. Comparison between the XRD patterns of powder and the thin films of TiOPc suggests that the molecule orients perpendicular to the glass substrate. g-tensor components and an angular variation of the EPR spectra reveal that TiOPc orients in the vicinity of the substrate normal. The EPR spectra demonstrated that the molecular orientation is dependent upon the deposition period. Angular variation of the EPR linewidth indicates two-dimensional spin-chain interactions in the vacuum-deposited films, reflecting a planar network of the spin-chains, Thermal annealing for 2 h induced an orientation change in the films where TiOPc reorients from the parallel to perpendicular positions with respect to the substrate.