We report the fabrication of superhydrophobic surfaces with a hierarchical morphology by self-organized anodizing process. Simply by anodizing of niobium metal in hot phosphate-glycerol electrolyte, niobium oxide microcones, consisting of highly branched oxide nanofibers, develop on the surface. The size of the microcones and their tip angles are controlled by changing the applied potential difference in anodizing and the water content in the electrolyte. Reduction of the water content increases the size of the microcones, with the nanofibers changing to nanoparticles. The size of microcones is also reduced by increasing the applied potential difference, without influencing the tip angle. The hierarchical oxide surfaces are superhydrophilic, with static contact angles close to 0 degrees. Coating of the anodic oxide films with a monolayer of fluoroalkyl phosphate makes the surfaces superhydrophobic with a contact angle for water as high as 175 degrees and a very small contact angle hysteresis of only 2 degrees. The present results indicate that the larger microcones with smaller tip angles show the higher contact angle for water. (C) 2011 Elsevier Ltd. All rights reserved.