A self-relay rhodium(I)-catalyzed cyclization of alkyne-azides with two σ-donor/π-acceptor ligands (isonitriles and CO) to form sequentially multiple-fused heterocycle systems via tandem nitrene transformation and aza-Pauson-Khand cyclization has been developed. In this approach, an intriguing chemoselective insertion process of isonitriles superior to CO was observed. This reaction provides an alternative strategy to synthesize functionalized pyrrolo[2,3-b]indole scaffolds.