The reactions of anhydrous gold() chloride [AuCl 3 ] 2 with aromatic hydrocarbons (ArH) such as benzene, toluene, xylenes, mesitylene, cumene, methoxybenzene and chlorobenzene, and the following treatment with 2,6-lutidine (lut) gave stable arylgold() complexes [AuArCl 2 (lut)]. These auration reactions proceeded heterogeneously in hexane and homogeneously in diethyl ether. The 1 H NMR spectra of the arylgold() complexes revealed that aurations towards aromatic compounds take place regiospecifically at the position with higher electron density and with less steric hindrances. The trans configuration of the arylgold() complexes was established by means of their far-IR spectra and confirmed for [Au(2,5-Me 2 C 6 H 3 )Cl 2 (lut)] by its single-crystal X-ray structure. The reactions of [AuArCl 2 (lut)] (Ar = phenyl, 2,5-xylyl) with a terminal alkyne, phenyacetylene (HC᎐ ᎐ ᎐ CPh), afforded arylated phenylacetylenes ArC᎐ ᎐ ᎐ CPh.