Luminescence is one of the most important properties for metal nanoclusters; however, clearly revealing its origin remains challenging. The different luminescence properties of the two prototypical 8e nanoclusters Au11 and Au13 remain elusive—Au11 is always nonluminescent, whereas Au13 is luminescent. In this work, by using a designed unique aromatic ligand (quinoline-2-thiol), we obtained new atomically precise phosphine-thiolate-protected neutral Au11-SH and cationic Au13-SH. In comparison with the classic phosphine-halide-protected Au11-Cl and Au13-Cl, the Cl-to-thiol alteration triggered room-temperature luminescence of the Au11 core and dramatically modulated that of the Au13 core. Ultrafast ultraviolet/infrared (UV/IR) spectroscopy, which is sensitive to organic aromatic groups, together with ultrafast transient absorption (TA) spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters. This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands, which would have direct applications in lighting, light harvesting, and photocatalysis.