The gold complexes n-Bu4N[Au(α-tpdt)2] (5), n-Bu4N[Au(dtpdt)2] (4) and n-Bu4N[Au(tpdt)2] (6) based on new dithiothiophene ligands (α-tpdt=2,3-thiophenedithiolate, dtpdt=2,3-dihydro-5,6-thiophenedithiolate and tpdt=3,4-thiophenedithiolate) have been prepared and characterised. These gold(III) complexes are diamagnetic, but they can be oxidised with iodine to the paramagnetic compounds [Au(α-tpdt)2] (8), [Au(dtpdt)2] (7) and n-Bu4N[{Au(tpdt)2}n∼2] (9), which were isolated as fine powders and which exhibit paramagnetic susceptibilities that are almost temperature independent with room temperature values of 2.5×10−4, 2.0×10−4 and 5×10−4 emu mol−1, respectively. Interestingly, the neutral complex [Au(α-tpdt)2] (8) as a polycrystalline sample displays the properties of a metallic system with a room temperature electrical conductivity of 6 S cm−1 and a thermoelectric power of 5.5 μV K−1; this is the first time that this metallic property has been observed in a molecular system based on a neutral species.