We have demonstrated a facile fabrication of copper oxide hierarchical structures on copper substrates by the oxidation of copper in hot alkaline solutions. The flowerlike hierarchical structures are synthesized by simply immersing a copper substrate into ammonium hydroxide alkaline solutions and heating at a particular temperature. The wettability of the surface was changed by chemical modification with 1H,1H,2H,2H-perfluorooctyltrichloro silane. We also discuss the effect of heating time on the morphology of the as-prepared copper oxide and hydrophobicity/oleophobicity. It is a unique method to generate both superhydrophobic and superoleophobic conditions in the same copper plate. The developed fabrication procedures allow the large area, cost-effective fabrication of copper oxide films. Our method might provide a general route towards the preparation of novel hierarchical films on metal substrates for various industrial applications including fluid transfer, fluid power systems, stain resistant, and antifouling.