Vacuum deposited vanadyl naphthalocyanine (VONc) crystalline thin films were produced. The films showed a completely different structural and growth pattern on thermal annealing and gamma-ray irradiation. The XRD spectra revealed polycrystalline nature for both annealed and gamma-ray irradiated films. Raman spectra observes that the gamma-irradiated films had a higher disorder producing broad and diffuse peaks in comparison to its annealed samples. In the absorption spectra, the gamma-irradiated films shows a broad Q-band with a shift of 50 nm towards the IR region enabling VONc to be used in a lot of applications using the commercially available semiconductor NIR lasers. Films on 97.9 krad gamma-ray irradiation showed some interesting properties with a better conductivity compared to either it's higher gamma-ray irradiated counterpart (195.8 krad) or the annealed films. Also the activation energy values, which is the minimum amount of energy required to liberate charge carriers from traps or to ionize levels within the band gap, was found to be lowered to half of its value for the films irradiated at 97.9 krad promising its performance in optical data recording, photo-sensitizer in photodynamic therapy, etc.