Abstract: Nanostructured Pt electrodes were prepared by electrodeposition of Pt nanoparticles on different substrates (GC, Pt and Au) under cyclic voltammetric conditions and with various number (n) of potential cycling, and were denoted as nm-Pt/S(n) (S=GC, Pt and Au). Adsorption of (bi)sulfate on the nm-Pt/S(n) was studied by in situ FTIR reflection spectroscopy. It has been revealed that the nanostructured Pt electrodes exhibit anomalous IR properties for (bi)sulfate adsorption regardless of the different reflectivity of substrate, i.e. the IR absorption of (bi)sulfate species adsorbed on all the nm-Pt/S(n) electrodes is significantly enhanced and the IR band direction is completely inverted in comparison with the same species adsorbed on a bulk Pt electrode. The two IR bands around 1200 and 1110cm−1 attributed to adsorbed (bi)sulfate species are shifted linearly with increasing electrode potential, yielding Stark tuning rates () of 152.1 and 21.1cm−1 V−1 on nm-Pt/GC(20), respectively. Along with increasing n, the Stark tuning rate of the IR band around 1200cm−1 decreases quickly and declined to 7.6cm−1 V−1 on nm-Pt/GC(80), while the Stark tuning rate of the IR band near 1100cm−1 is fluctuated between 23.0 and 16.2cm−1 V−1. It has determined that the enhancement of IR absorption of (bi)sulfate adsorbed on nanostructured Pt electrode is varied with substrate material and n, and a maximal 16-fold enhancement of the IR band near 1200cm−1 has been measured on the nm-Pt/GC(30) electrode. The in situ FTIR studies illustrated that the adsorption of (bi)sulfate occurs mainly in the double layer potential region, and reaches a maximum around 0.80V. The results demonstrated also that the competitive adsorption of CO and oxygen species can inhibit completely (bi)sulfate adsorption, which has evidenced a weak interaction of (bi)sulfate with nm-Pt/S(n) electrode surface. [Copyright &y& Elsevier]