The anionic hydroxyethyl-substituted gold dithiolene complex [NEt4][Au(EtOH-thiazdt)(2)] is synthesized and further oxidized to the neutral radical species [Au(EtOH-thiazdt)(2)] through electrocrystallization. Single-crystal X-ray diffraction studies highlight the existence of the two cis and trans isomers for the monoanionic complex, with involvement of the hydroxy group in intermolecular O-H center dot center dot center dot S hydrogen-bonding interactions. The neutral radical complex, [Au(EtOH-thiazdt)(2)](center dot), is isostructural with its known ethyl analogue, namely, [Au(Etthiazdt)(2)](center dot). It exhibits a semiconducting behavior (sigma(RT) = 0.05-0.07 S cm(-1)) at room temperature and ambient pressure with an activation energy of 0.14 eV. Comparison of the crystal structures and transport and magnetic properties with those of the prototypical [Au(Et-thiazdt)(2)](center dot) single-component conductor shows that the replacement of ethyl by a slightly bulkier hydroxyethyl substituent affects only weakly the overlap interactions, complemented here by added O-H center dot center dot center dot S hydrogen-bonding interactions.