Hierarchical CuO nanostructures (urchin-like and grassy island structure) were successfully synthesized by a simple chemical bath deposition method at low temperature of 70°C in a short reaction time of 1h. XRD analysis revealed the presence of pure crystalline monoclinic CuO. Morphological analysis revealed the formation of spherical structures composed of numerous hair-like structures. The pH of the solution was also investigated to have a great effect on the morphology of the CuO nanostructures. At lower pH, the structures tend to form urchin-like structures; while at higher pH, the structures tend to form grass-like islands. A growth mechanism was also proposed in this paper. Lastly, wettability test proved the stable superhydrophobic property of the CuO nanostructured thin film surface.