Effects of Cetyl Trimethyl Ammonium Bromide (CTAB), which is a kind of cationic surfactants, and Sodium Dodecyl Sulfate (SDS), which is a kind of anionic surfactants on the anodic formation of nanoporous niobium oxide were compared. The addition of SDS could protect the surface from dissolution for long time, leading to the formation of niobium oxide with a double thickness (~400 nm) compared to that prepared without surfactant, whereas dissolution seriously occurred in the solution containing CTAB. The different behaviors were attributed to the interaction between the surfactants with positive (or negative) charge and positively charged niobium oxide.