Ion mobility mass spectrometry (IM-MS) can separate ions based on their size, shape, and charge as well as mass-to-charge ratios. Here, we report experimental IM-MS and IM-MS/MS data of the Au(25)(SCH(2)CH(2)Ph)(18)(-) nanocluster. The IM-MS of Au(25)(SCH(2)CH(2)Ph)(18)(-) exhibits a narrow, symmetric drift time distribution that indicates the presence of only one structure. The IM-MS/MS readily distinguishes between the fragmentation of the outer protecting layer, made from six [-SR-Au-SR-Au-SR-] "staples' where R = CH(2)CH(2)Ph, and the Au(13) core. The fragmentation of the staples is characterized by the predominant loss of Au(4)(SR)(4) from the cluster and the formation of eight distinct bands. The consecutive eight bands contain an increasing variety of Au(l)S(m)R(n)(-) product ions due to the incremental fragmentation of the outer layer of Au(21)X(14)(-), where X = S or SCH(2)CH(2)Ph. The mobility of species in each individual band shows that the lower mass species exhibit greater collision cross sections, facilitating the identification of the Au(l)S(m)R(n)(-) products. Below the bands, in the region 1200-2800 m/z, product ions relating to the fragmentation of the Au(13) core can be observed. In the low mass 50-1200 m/z region, fragment ions such as Au(SR)(2)(-), Au(2)(SR)(3)(-), Au(3)(SR)(4)(-), and Au(4)(SR)(5)(-) are also observed, corresponding to the large fragments Au(25-x)(SR)(18-(x+1)). The study shows that most of the dominant large fragments are of the general type Au(21)X(14)(-/+), and Au(17)X(10)(-/+) with electron counts of 8 and 6 in negative and positive mode, respectively. This suggests that geometric factors may outweigh electronic factors in the selection of Au(25)(SR)(18) structure.