In this multidisciplinary study the chemical reduction synthesis of novel gold clusters in solution was combined with high-resolution analytical mass spectrometry (MS) to gain insight into the composition of the gold clusters and how their size, ionic charge state, and ligand substitution influences their gas-phase fragmentation pathways. Ultrasmall cationic gold clusters ligated with 1,3-bis(dicyclohexylphosphino)propane (dcpp) were synthesized for the first time and introduced into the gas phase using electrospray ionization (ESI). Mass-selected cluster ions were fragmented by employing collision-induced dissociation (CID) and the product ions were analyzed using MS. The solutions were found to contain the multiply charged cationic gold clusters Au9L43+, Au13L53+, Au6L32+, Au8L32+, and Au10L42+ (L=dcpp). The gas-phase fragmentation pathways of these cluster ions were examined systematically by employing CID combined with MS. In addition, CID experiments were performed on related gold clusters of the same size and ionic charge state but capped with 1,3-bis(diphenylphosphino)propane (dppp) ligands containing phenyl functional groups at the two phosphine centers instead of cyclohexane rings. It is shown that this relatively small change in the molecular substitution of the two phosphine centers in diphosphine ligands (C6H11 versus C6H5) exerts a pronounced influence on the size of the species that are preferentially formed in solution during reduction synthesis as well as the gas-phase fragmentation channels of otherwise identical gold cluster ions. The mass spectrometry results indicate that in addition to the length of the alkyl chain between the two phosphine centers, the substituents at the phosphine centers also play a crucial role in determining the composition, size, and stability of diphosphine-ligated gold clusters synthesized in solution.