The stability and H 2 adsorption activity of bimetallic Au 79− n Pd n (n=1–55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face>mid-edge>corner>edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H 2 adsorption activity is corner≈edge>mid-edge>face. The Au 36 Pd 43 (3) with Au:Pd≈1:1 ratio and twenty-four Pd substitutions at (111) facets and nineteen Pd substitutions at subshell sites shows high stability and H 2 non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ε d and the adsorption energies, the ε d order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites.