The study of the catalytic activity of carbon supported Pd-Ni catalysts for the hydrodechlorination of hexachlorobenzene was carried out in the liquid phase. The degree of dechlorination was found proportional to the surface Pd concentration, which is enhanced by the segregation of this element at the surface of the bimetallic particles. It is also shown that isolated Pd atoms located at the surface of Ni rich bimetallic particles are more active than those lying in larger ensembles. Finally bimetallic Pd-Ni catalysts containing only between 20 and 50 Pd atom%, although less active than pure Pd, lead to 75% of useful compounds, i.e. benzene, mono and dichlorobenzene.