We present in this work a comprehensive investigation of the role played by dissolved tetrafluoroboric acid on the electrochemical response of a polycrystalline platinum electrode in acidic media. HBF4 from two different suppliers was employed and characterized in terms of the amount of arsenic contamination by Inductively Coupled Plasma-Optical Emission Spectroscopy. The effect of different amounts of HBF4 on the voltammetric profile of the Pt vertical bar HClO4(aq) interface was investigated by means of electrochemical quartz crystal nanobalance (EQCN). Despite the comparable cyclic voltammograms, the presence of arsenic in one of the two HBF4 used resulted in dramatic variations in the mass change profile, which evidences the deposition/dissolution of arsenic prior to the surface oxidation. For the arsenic-free HBF4, its effect on the mass change profile was mainly associated to anion adsorption. The impact of dissolved HBF4 on the electro-oxidation of formic acid was rationalized in terms of two contributions: current enhancement at low potentials due to the arsenic-assisted formic acid electro-oxidation and inhibition at high potentials due to anion adsorption. (C) 2011 Elsevier B.V. All rights reserved.