A novel class of compounds bearing indole and benzimidazole rings was designed and easily synthesized from 2-indolecarboxylic acid and ophenylenediamine.The catalytic system derived from a 2indolylbenzimidazole-based ligand and Pd(OAc) 2 in situ could lead to complete conversion of aryl bromides at 0.5 mol% Pd loading under mild reaction conditions. In the presence of a catalyst, sterically hindered biaryls were selectively generated in excellent yields by adjusting reaction parameters through the coupling of arylboronic acids with aryl halides. The efficiency of this reaction was demonstrated by its compatibility with various functional groups.