The dissociative adsorption and oxidation behavior of HCOOH on Pt was investigated by cyclic voltammogram (CV) and in-situ surface enhanced Raman spectroscopy (SERS) techniques. The in-stiu SERS of HCOOH adsorption, dissociation and oxidation on rough Pt is reported. It is found that HCOOH can spontaneously dissociate. The surface Raman spectra of CO, the strongly adsorbed intermediate and COOH, the weakly adsorbed intermediate of the dissociative adsorption of HCOOH were successfully obtained for the first time. At the same time, the Raman spectra of the finally oxidized product CO2 of HCOOH was also firstly detected. The dual path reaction mechanism for the oxidation of HCOOH was confirmed at molecular level