A series of dimeric gold(I) complexes L 2 Au 2 Cl 2 has been synthesized by the reaction of equimolar amounts of 10-(aryl)phenoxarsine ligands with chloro(tetrahydrothiophene)gold(I). The structure of complexes 4 – 6 has been confirmed by a combination of physicochemical methods. The crystal structure of complex 4 has been determined by single-crystal X-ray diffraction. The Tolman angles have been calculated for the known tertiary arsine ligands and the ligands in the synthesized gold complexes. It has been shown that the dimeric structure of the complexes is formed through the aurophilic interaction between two monomers. The Tolman angle of the phenoxarsine ligand plays a significant role in this interaction; in the dimeric complexes, this angle is on average 147°.