A site-selective spectroscopy study of Ag nanoclusters dispersed in oxyfluoride glass hosts has been carried out. The nano- to millisecond, essentially non-exponential, luminescence kinetics of Ag nanoclusters has been detected in the spectral range from 450 to 1000 nm, when excited at discrete wavelengths in the range 250 to 450 nm. Based on these experimental observations, the energy level configuration coordinate diagram for the involved ground and excited singlet/triplet states of the Ag nanoclusters has been proposed and confirmed by the density functional theory (DFT). The sites for the Ag nanoclusters are argued to be multiple. The structure/geometry of the involved Ag nanoclusters has been suggested to involve spin-paired dimers Ag²⁺, or tetramers Ag₄²⁺, with a varying elongation/distortion along the tetramer diagonals.