In this paper, we report on the three-dimensional nanostructured Cu2O/CuO films with controlled flower-like shapes using a direct crystallization approach in the presence of sodium borohydride without using any performed template, surfactant or oxidant. The microstructures and shapes of Cu2O/CuO architectures were investigated by field emission scanning electron microscopy, X-ray diffraction and transmission electron microscopy. Three types of chrysanthemum-like, candock-like and dandelion-like CuO microstructures consisting of densely packed building blocks of nanobelts or nanoribbons were achieved by governing the concentrations of NaBH4. Possible growth mechanisms for the controlled organization of primary building units into three-dimensional flower-like architectures were proposed. After simple surface modification with sodium laurate, the resulting films displayed hydrophobic and even superhydrophobic properties owing to their special surface nano-/microstructures. (c) 2011 Elsevier B.V. All rights reserved.