Given that biaryl motifs are found in many useful molecules, including pesticides, pharmaceuticals, functional materials, and polymers, the development of methods for their construction is important. Herein, we report a two-step method for C(sp2)-H/C(sp2)-H cross-coupling reactions to synthesize 2-arylindole derivatives by combining palladium catalysis and photocatalysis. This mild, dual-catalysis method showed good functional group tolerance and a wide substrate scope and could be used for late-stage functionalization of oligopeptides, drugs, and natural products.