A bismuth-film electrode (BiFE) was applied in square-wave anodic stripping voltammetry (SWASV) in order to determine Sn (IV) in biodiesel samples. In situ simultaneous deposition of tin and bismuth at -1.2V for 90s was carried out in a supporting electrolyte containing 0.1 mol L-1 acetate buffer (pH 4.5) and 1.73 mmol L-1 caffeic acid as the complexing agent. A single well-defined anodic stripping peak was observed at -0.58 V for the oxidation of Sn to Sn (II), which was used as the analytical signal. The calibration curve was obtained in the concentration range of 0.17-7.83 mu mol L-1 with the detection limit being 0.14 mu mol L-1 (r = 0.9990). Repeatability and reproducibility for the measurement of the current peak were characterized by relative standard deviations of 3.6% and 4.1%, respectively, for a 5.0 mu mol L-1 Sn (IV) solution (n = 10). The method was validated by comparing the results obtained with those provided by application of the atomic absorption spectroscopy technique. (C) 2011 Elsevier Ltd. All rights reserved.