The crystal structure of the [Ag62S12(SBut)32](2+) nanocluster (denoted as NC-I) has been successfully determined, and it shows a complete face-centered-cubic (FCC) Ag14 core structure with a Ag-48(SBut)32 shell configuration interconnected by 12 sulfide ions, which is similar to the [Ag62S13(SBut)32](4+) structure (denoted as NC-II for short) reported by Wang. Interestingly, NC-I exhibits prominent differences in the optical properties in comparison with the case of the NC-II nanocluster. We employed femtosecond transient absorption spectroscopy to further identify the differences between the two nanoclusters. The results show that the quenching of photoluminescence in NC-I in comparison to that of NC-II is caused by the free valence electrons, which dramatically change the ligand to metal charge transfer (LMCT, S 3p -> Ag 5s). To get further insight into these, we carried out time-dependent density functional theory (TDDFT) calculations on the electronic structure and optical absorption spectra of NC-I and NC-II. These findings offer a new insight into the structure and property evolution of silver cluster materials.