In the design of ligand-protected metal clusters, the choice of protecting ligands is a critical factor because they can profoundly affect the nuclearity, geometry, and electronic structures to afford a diverse range of cluster compounds. Here, we report the synthesis of two novel diarsine-protected Au13 clusters ([Au13L5Cl2]3+, L = diarsine) and compare these clusters with diphosphine analogs in terms of the core geometry and optical properties. In the crystal structure, the cluster bearing C3-bridged diarsines {[Au13(dpap)5Cl2]3+, 3} had an apparently identical icosahedral Au13 core to [Au13(dppe)5Cl2]3+ (1) with C2-bridged diphosphines, but slight structural differences associated with the bridging unit of the ligands were found. Despite similar icosahedral Au13 cores 1 and 3, their absorption and photoluminescence profiles were evidently different. Theoretical calculations revealed that the subtle deformation of the Au13 icosahedron, rather than the coordinating atoms (As or P), notably influences the electronic structure to cause the difference in the absorption profiles.