Co-adsorption of nitromethane at Pt electrodes, and its influence on HCOOH electrocatalytic oxidation were investigated by cyclic voltammetry and potentiostatic quasi-steady state polarization curves. Potentiodynamic I/E curves in the presence of nitromethane show a considerable current increase in the low potential region (0.2–0.5 V). This effect is maintained under quasi-steady state conditions.Electrosorption studies performed with nitromethane indicated that partially reduced species are adsorbed on the electrode surface. These species could be responsible for the observed promoting effect. The results obtained with nitromethane addition are compared with acetonitrile and dimethylsulfoixide. Competition for adsorption sites and modifications of surface adsorption energy produced by additive adsorption, account for their specific influence on the HCOOH oxidation rate.