The catalytic voltammetric protocol for the determination of titanium at a bismuth film electrode is presented. The method is based on the reduction of the Ti(IV)-oxalate complex to Ti(III)-oxalate in an acidic solution. It was proven that the addition of KClO 3 causes rapid oxidation of Ti(III)-oxalate and, subsequently, an increase of the reduction peak current of Ti(IV) at the bismuth film electrode. Parameters that influence the Ti response, including the film preparation, solution pH, oxalate acid and chlorate concentrations, were optimized. The exploitation of the bismuth film electrode under the optimized conditions yielded a stable response for titanium, with high sensitivity (12.5 mA mM À1 ), good precision (RSD ¼ 5.0%) and a low detection limit (1 Â 10 À8 M).