Abstract <p>This work reports a novel strategy for achieving antireflective properties through the fabrication of nanostructured TiO₂ thin films by controlled wrinkling under ultra-high vacuum (UHV) conditions. The approach is based on a designed bilayer system consisting of a titanium dioxide (TiO₂) coating deposited on a dodecaphenyl-POSS scaffold, which generates a well-defined wrinkled nanostructure with enhanced light-scattering capability. Structural characterization by Grazing Incidence X-ray Diffraction (GIXRD) and Raman spectroscopy confirmed the coexistence of anatase and rutile phases, as well as a clear phase transformation influenced by annealing temperature. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) analyses further elucidated the evolution of surface morphology, revealing a systematic decrease in wrinkle density and amplitude with increasing annealing temperature and TiO₂ thickness. Optical measurements demonstrated a significant reduction in reflectance, with over 58% improvement compared to bare silicon substrates. These results highlight the potential of nanostructure-induced surface modification to improve optical performance and provide a promising pathway for applications in solar energy conversion, photonic coatings, and other energy-related technologies.</p> Graphical abstract <p></p>