A series of Pt/Al2O3 catalysts were prepared by the impregnation method and were characterized by TEM, XRD, H2 and CO chemisorptions, and investigated in the hydrodechlorination of tetrachloromethane. Three Pt-rich, Pt–Au/Al2O3 catalysts (Pt100, Pt95Au5 and Pt90Au10) showed a similar metal particle size (~2.5–2.7 nm), so observed changes in the catalytic behavior are ascribed to alloying effect, especially because a considerable degree of Pt–Au mixing was achieved in the bimetallic samples. It appeared that by introducing very small amount of gold (10 at.%) to platinum, the catalytic activity is increased. It is argued that the occurrence of this moderate synergistic effect is associated with a decreased tendency of surface chloriding when platinum is alloyed with gold.