The preparation of materials with aligned porosity in the nanometer range is of technological importance for a wide range of applications in molecular filtration, biomaterials and catalysis. Herein we present the advantages offered by cryo - lyophilisation technique as a smart and green non-standard concept to produce dense regular polyhedral nanocavities inside the 2D TiO2 nanosheets. Hierarchical morphologies of nanocavities start to appear at temperature higher than 800 degrees C and are strongly influenced by polymorph TiO2 evolution competing reactions. The small angle X-ray scattering (SAXS) analysis confirms self-assembled 3D nanocavities with size range from 5 to 10 nm in both length and width, and depth (similar to)3.6 nm formed after realising of the confined icewater. It was found that nanocavities enhance significantly the absorption properties of TiO2 in the UV region, thereby providing a new approach to increase the photoreactivity of 2D TiO2 nanosheets. The annealed precursors containing aqueous solution of peroxo polytitanic acid (PPTA) at 800 degrees C exhibited the highest photoactivity in degrading bisphenol A (BPA) due to evenly distributed nanocavities inside single anatase TiO2 nanocrystals interconnected and aligned onto the 2D TiO2 nanosheet arrays.