Nanostructured Bi12TiO20 coatings with superior photocatalytic property were controllably fabricated on bismuth substrates by one-step electrochemical method in the alkali electrolytes. It was found that the high voltage spark, which initiated the transformation of Bi2O3 precursor generated at low voltage to sillenite type Bi12TiO20, dominated the formation of bismuth titanate coating. Varying the deposition voltage can effectively tailor the crystallinity, morphology and optical property of the coatings. Bi12TiO20 coating consisting of spherical particles of ca. 30nm in size and micropores of ca. 100nm in diameter was obtained at voltage 80V, exhibiting enhanced visible spectrum absorption and higher photocatalytic ability compared to pure TiO2 films prepared with similar electrochemical method.