Oriented NiAl-layered double hydroxide (LDH) films with micro-/nanometer scale binary structures are prepared by in situ crystallization, without using any external aluminum source or shape-directing surfactant, on a porous anodic alumina/aluminum substrate. The NiAl-LDH film structures can be controlled by tuning crystallization temperature and time. Facile hydrophobic modification of the film surface leads to superhydrophobicity, as shown in the figure.