The fluxional nature of small gold clusters has been exemplified by reversible isomerization between [Au-9(PPh3)(8)](3+) with a crown motif (Au-9(C)) and that with a butterfly motif (Au-9(B)) induced by association and dissociation with compact counteranions (No-3(-), Cl-). However, structural isomerization was suppressed by substitution of the central Au atom of the Au-9 core in [Au-9(PPh3)(8)](3+) with a Pd atom: [PdAu8(PPh3)(8)](2+) with a crown motif (PdAu8(C)) did not isomerize to that with a butterfly motif (PdAu8(B)) upon association with the counteranions. Density'functional theory calculation showed that the energy difference between PdAu8(C) and PdAu8(B) is comparable to that between Au-9(C) and Au-9(B), indicating that the relative stabilities of the isomers are not a direct cause for the suppression of isomerization. Temperature dependence of Debye-Waller factors obtained by X-ray absorption fine-structure analysis revealed that the intracluster bonds of PdAu8(C) were stiffer than the corresponding bonds in Au-9(C). Natural bond orbital analysis suggested that the radial Pd-Au and lateral Au-Au bonds in PdAu8(C) are stiffened due to the increase in the ionic nature and decrease in electrostatic repulsion between the surface Au atoms, respectively. We conclude that the formation of stiffer metal-metal bonds by Pd atom doping inhibits the isomerization from PdAu8(C) to PdAu8(B).