Abstract Combining hard‐templating and infiltration processes, micro‐ and nanoscale topography induced by 2D assembling of TiO 2 nanoparticles is extended to 3D TiO 2 . By applying an ultrathin and highly conformal polytetrafluoroethylene (PTFE) layer on prepared 3D TiO 2 via initiated chemical vapor deposition (iCVD), a robust superhydrophobic bulk material (3D PTFE/TiO 2 ) is achieved. A comparative study is conducted to reveal the stability of Cassie state for 3D PTFE/TiO 2 against the external pressure by squeezing a water droplet between 2D and 3D PTFE/TiO 2 structures. The use of such a stable 3D superhydrophobic PTFE/TiO 2 structure for the controlled release medium is shown by a case study.