Photoluminescence and Raman results for single crystals of KCl doped with KAu(CN)(2) with different Au content are presented and compared with results for pure KAu(CN)(2) crystals. Photoluminescence spectra of the doped crystals show three major UV-vis bands that can be resolved by varying the excitation wavelength. Spectroscopic and computational evidence suggests the formation of Au-Au bonded excimers and exciplexes in this doped system. The excimer/exciplex luminescence bands can be tuned in a given crystal by siteselective excitation and their relative intensities tuned by varying the dopant concentration. Microsecond lifetimes were observed for the various luminescence bands, suggesting Au-centered phosphorescent emissions. Raman spectral analysis was used successfully to correlate with the luminescence bands observed in pure and doped crystals of [Au(CN)(2)(-)] and [Ag(CN)(2)(-)] systems. The Raman vCN bands corresponding to various sites of [Au(CN)(2)(-)](n) and [Ag(CN)(2)(-)](n) clusters in various crystals correlated well with the luminescence spectra, in terms of both the number of peaks and their relative frequencies. The results have illustrated interesting differences in the clustering of [Au(CN)(2)(-)] versus [Ag(CN)(2)(-)] ions in the host lattice, As the dopant level increases, the extent of metal-metal interactions increases due to larger oligomers or shorter metal-metal separation, in either case leading to decreased back-bonding and higher vCN frequencies, The vCN Raman frequencies in [Au(CN)(2)(-)]/KCl crystals with increasing doping level increased beyond the value for pure KAu(CN)2 crystals, presumably due to a shorter Au-Au distance in the highest doped crystal than the distance in the pure crystal. In contrast, increasing the doping level in [Ag(CN)(2)(-)]/KCl systems resulted in the appearance of vCN Raman peaks with correspondingly higher frequencies but the values remained lower than those for pure KAg(CN)(2) crystals, as expected.