The anodic behaviour of bismuth in aqueous p-toluenesulfonic acid at three different concentrations and in the potential range from 0 to 1.0 V is studied. A significant amount of white precipitate on the bismuth surface is synthesized at selected potentials. The morphology and elemental composition of the anodic layers are observed using SEM and EDS, respectively. The composition and crystallinity of the product at 1.0 V are determined using FT-IR, ICP, XPS and XRD analytical methods. The composition of the anodic product is compared with that of an already known product synthesized via a chemical reaction between Bi₂O₃ and p-toluenesulfonic acid. The results show that the anodic product has a composition of [Bi₆O₄(OH)₄](C₇H₇SO₃)₆. Hence, this product can be prepared via electrochemical synthesis by the potentiostatic polarization of bismuth at 1.0 V.