The photochemistry of a gold(I) thiocyanate complex has been investigated to determine the coordination structure in both the solid and liquid states. The coordination geometries of the supramolecular [Au(SCN)(2)](n) complex and the concomitant exciplex have mainly been analyzed by crystallographic analysis and X-ray absorption spectroscopy. The Au-S bond distance and Au...Au separation of the compound in the S-0 ground state and in the T1 phosphorescent excited state (lambda(ex) = 340 nm) were compared. Upon irradiation with UV light, the excimeric interactions were enhanced, resulting in a contraction of the Au-I...Au-I aurophilic distance by 0.0113(4) angstrom. A broad luminescence spectrum was observed for the one-dimensional chain suprastructure. The time-resolved luminescence spectra indicated the entity of several oligomeric species in the crude liquid without neutral solvent molecules. In addition, extended X-ray absorption fine structure spectroscopy exhibited a slight change in the nearest AuS distance due to the photoswitched transformation. The deformation of the (Au---Au)* exciplexes was not apparently promoted in the liquid state with the asymmetrical imidazoium cations having a nonlocal charge distribution in the present observation. This is plausibly due to a flexible molecular structure and a property in the liquid state. In conclusion, the photoexcited nature of the pseudo-one-dimensional complexes has emerged in controlling bond distances among the supramolecular networks.