Four polymorphic forms of the complex Zn[Au(CN)(2)](2) have been synthesized and both structurally and spectroscopically characterized. In each of the four polymorphs, a zinc center in a tetrahedral geometry with a Au(CN)(2)(-) unit at each tetrahedral vertex is observed. All four structures contain three-dimensional networks based on corner-sharing tetrahedra. Because of the long Au(CN)(2)(-) bridging unit, the extra space not occupied by one network is filled by two to five additional interpenetrated networks. Short gold-gold bonds with lengths ranging from 3.11 to 3.33 angstrom hold the interpenetrated networks together. Three of the four polymorphs are luminescent, having solid-state emissions with wavelengths ranging from 390 to 480 nm. A linear correlation between the emission energy and the gold-gold distance was observed. Upon exposure to ammonia vapor, the polymers altered their structures and emission energies, with the emission wavelength shifting to 500 nm for {Zn(NH3)(2)[Au(CN)(2)](2)}, which adopts a two-dimensional layer structure with octahedral, trans-oriented NH3 groups. The adsorption route is dependent on the polymorph used, with NH3 detection limits as low as 1 ppb. Desorption of the ammonia occurred over 30 min at room temperature.