XPS, temperature-programmed reaction and HREELS have been used to study the adsorption and reactions of acetic acid on Pd{111}. At 170 K the adsorbed monolayer contains intact and dissociated acetic acid molecules, the latter consisting of a mixture of bidentate acetate and another species tentatively identified as monodentate acetate. The monodentate acetate appears to resemble closely the acetate species observed under reaction conditions at the surface of a pure palladium vinyl acetate synthesis catalyst. Thermal decomposition of the adsorbate yields CO2, H2O, CO, H-2 and carbon. The associated processes may be rationalised in terms of two reaction channels, one due to the monodentate and the other due to the bidentate acetate.