Highly oriented Vanadyl-Phthalocyanine (VOPc) thin film fabricated on Au (111) substrate has recently been attracting much attention in the fields of nanoelectronics and optoelectronics. Orientation control of VOPc thin film prepared on Au (111) substrate was performed by annealing treatment. The deposition process of VOPc thin film fabricated on Au (111) substrate involves three different phases. The initial deposition layer is epitaxially grown on Au (111), the next layer is the quasiepitaxial layer (pseudomorphic layer) and the final layer is the monoclinic layer (bulk layer). The quasiepitaxial layer treated with annealing transforms from the quasiepitaxial layer to the epitaxial layer. However, the morphology of the monoclinic layer is not changed by the annealing treatment.