The ion‐assisted vapor deposition (IAD) method is utilized to prepare silicone polymer thin films with low surface energy. Methacryl‐modified silicone oligomer is deposited under irradiation of argon ions with various ion energies and currents. Fourier transform infrared analysis and solvent durability test reveal that the polymerization reaction is enhanced with increasing ion energy. Smooth and insoluble films are obtained under ion irradiation at the energy of 1 kV. The films have surface free energy of about 26 mJ m−2, and the peeling strength of an adhesive tape on their surface can be controlled by the ion current of IAD. X‐ray photoelectron spectroscopy analysis shows that the ion irradiation induces dissociation of methyl side groups and cross‐linking by Si–O network formation, leading to an increase in the peeling strength and improvement in film robustness. The silicone films deposited by IAD have potential applicability to the anti‐adhesive surfaces.