In this study, we show that by anodization of Nb in NaF electrolytes microcone niobium oxide layers can be formed under a range of experimental conditions. It is found that a single NaF electrolyte leads to the formation of microcones. At 1 M NaF, 40 V, 1 h, well-ordered microcones were generated on Nb discs. XRD results show that the initially formed anodic oxide is amorphous, but an amorphous to crystalline transition occurs during anodization. For the formation of favorable microcones, it is considered that proper parameters such as electrolyte concentration, voltage, anodizing time are necessary according to the kind of electrolytes.