The effect of adding a third metal (Ni, Co, Pd, Rh) to Pt-Sn/C catalyst has been investigated for the adsorption and oxidation of acetic acid in acidic medium using in situ Fourier transform infrared (FTIR) spectroscopy. The results showed that the decomposition of acetic acid on the surface leads to the formation of different intermediate species and products such as acetate, acetyl, carbonate, CO and CO2. The reaction pathway of CO2 production proceeds via the formation of acetyl or carbonate through surface acetate species. It has been found that the selectivity of the acetate was enhanced by the addition of any third metal. However, the presence of Pd or Co increases the relative intensity of IR band for CO2. This is probably due to success in facilitating of the C-C bond cleavage of acetyl. On the other hand, the conversion of acetate to carbonate is strongly affected by the adsorbed water, as is evident from the pronounced changes in the OH stretching region with the presence of Pd or Ni.