Two mono-benzimidazolium salts of resorcinarene have been prepared and used as ligands in Suzuki-Miyaura cross-coupling reactions. They have been fully characterized by H-1 and C-13 NMR, MALDI, and FT-IR spectroscopic methods, and their structures were confirmed by X-ray diffraction analysis. These two new resorcinarene-based monobenzimidazolium salts showed good catalytic activity for coupling reactions in DMF. The highest conversion was achieved for arylation of 4-bromotoluene using the resorcinarenyl mono-dimethylbenzimidazolium salt.