Two series of highly dispersed supported Pd-Cu catalysts were prepared using different supports: highly acidic aluminum fluoride HS-AlF3, characterized by high surface area, and active carbon, both prepared by different preparation methods (fluorolytic sol-gel method and co-impregnation). A variety of techniques: chemisorption of hydrogen, XRD, TEM, and catalytic performance in two hydrogen-related probe reactions (in n-pentane hydroisomerization and CC14 hydrodechlorination) were employed to probe metal dispersion and the extent of interaction between two metal components. A reasonable degree of bimetal intermixing in Pd-CuIHS-AlF3 catalysts synthesized by fluorolytic co-gelation was recognized by the catalytic behavior in bifunctional hydroisomerization of n-pentane. A significantly decreased, compared to pure palladium, hydrogenation-dehydrogenation potential of Pd-Cu alloys led to a weaker performance of bimetallic catalysts. Similarly, it was found that incipient wetness co-impregnation of active carbon resulted in the formation of catalysts characterized by good metal dispersion and significant extent of Pd-Cu alloying. Although the monometallic 2 wt% Cu/carbon catalyst is nearly inactive in CCl4 hydrodechlorination, copper addition to palladium in the co-impregnated catalysts had very pronounced effect, vastly increasing the selectivity toward longer than methane hydrocarbons. (C0 2014 Elsevier B.V. All rights reserved.