Rhodacarborane [(9-NMe 3 -7,8-C 2 B 9 H 10 )RhCl 2 ] 2 exhibited moderate catalytic activity in the reaction of annulation of arylcarboxylic acids with alkynes, giving naphthalenes as the major products. Eff ects of the substituent at the carborane ligand, as well as the nature of organic substrates, on the catalytic activity and selectivity of the reaction were estimated. In particular, it was revealed that a replacement of the NMe 3 group at the carborane ligand with the SMe 2 one leads to a signifi cantly decreased activity of the catalyst.