Fluorescence and X-ray absorption spectroscopy were used to investigate the anion binding properties of a luminescent, dinuclear Au(i) N-heterocyclic carbene (NHC) complex (2+) with a short Au(i)⋯Au(i) contact. The addition of Br- ions to a DMSO solution of (PF 6)2 caused a red-shift in the fluorescence emission band from 396 nm to 496 nm. Similarly, the addition of Br- ions to (PF6)2 caused a decrease in the energy of the Au L 3-edge in the X-ray absorption spectrum, consistent with the formation of an association complex between the cation 2+ and Br- ions. Solution-based structural studies of the association complex were carried out using extended X-ray absorption fine structure (EXAFS) modelling of the Au(i)⋯Au(i) core of the cation. These studies indicate that the association complex results from Au(i)⋯Br- interactions, with the Br- ions occupying two partially occupied sites at ∼2.9 and 3.9 Å from the Au(i) atoms. © The Royal Society of Chemistry 2013.