The single-crystal X-ray structure of Pd-doped Au-25(SR)(18) was solved. The crystal structure reveals that in PdAu24(SR)(18), the Pd atom is localized only to the centroid of the Au-25(SR)(18) cluster. This single-crystal X-ray structure shows that PdAu24(SR)(18)(0) is well conceptualized with the superatom theory. The PdAu24(SR)(18)(+1) charge state is isoelectronic with Au-25(SR)(18)(+1) as determined by a first order Jahn-Teller effect of similar magnitude and by electrochemical comparison. The previously reported increased stability of PdAu24(SR)(18) can be rationalized in terms of Pd-Au bonds that are shorter than the Au-Au bonds in Au-25(SR)(18).