Crystals of the mixed-metal heterobi metallic Au/Ag dicyanide complex, K[AuxAg1-x(CN)(2)] (x = 0 -> 1), were obtained by slow evaporation. The mixed-metal complex K[Au0.44Ag0.56(CN)(2)] crystallizes in a rhombohedral crystal system, space group R (3) over bar. The crystal structure consists of layers of linear chains of Au(CN)(2)(-) and Ag(CN)(2)(-) ions and K+ ions that connect the layers through the N atoms. The excitation and emission spectra of single crystals of K[AuxAg1-x(CN)(2)] were recorded at 4.2-180 K using excitation wavelengths between 230 and 260 nm. Two emission bands due to Ag-Au interactions were observed at 343 and 372 nm. Lifetime measurements indicate the shorterwavelength emission corresponds to fluorescence and the longer-wavelength band is phosphorescence. These new emission bands are not seen in the pure K[Ag(CN)(2)] or pure K(Au(CN)(2)] crystals. Extended Huckel calculations show that the LUMO of the mixed-metal system is bonding while the HOMO is antibonding or very weakly bonding. Moreover, excited-state extended HOckel calculations indicate the formation of exciplexes with shorter metal-metal distances and higher metal-metal overlap populations than the corresponding ground-state oligomers. The luminescence is assigned to a mixed-metal transition from a molecular orbital with Au character to a molecular orbital with Ag character.