PtSn/Al2O3 catalysts with a given loading of 1 wt% Pt and 1 wt% Sn were prepared by co-impregnation or successive impregnation with aqueous solutions of Pt, Sn precursors and a commercial alumina. The catalysts were characterized by N2 adsorption, H2-TPR (H2 temperature-programmed reduction), H2-pulse chemisorption, XPS (X-ray photoelectron spectroscopy) and CO-FTIR (Fourier transform infrared spectroscopy), and tested in the hydrogenation of acetic acid. The results showed that the preparation method affected both the chemical properties and their performance in the hydrogenation of acetic acid. Sn enrichment on the catalysts surface was observed on the co-impregnated catalyst and catalyst in which the Pt precursor had been loaded first. It was found that the modification of Pt was a function of the sequence of Sn addition as revealed by CO-FTIR. Co-impregnated catalyst showed the highest activity and ethanol selectivity.