We have demonstrated the first ever example of nickel complexes as effective catalysts to promote the C–C, N–C cascade coupling of ketonitriles with arylboronic acids, affording potentially biologically active 3-carboxylate-2,5-diaryl-pyrroles as well as 2,5-diarylpyrroles and 2,6-diarylpyridines. This protocol features a broad scope of substrates and excellent functional group tolerance, thus representing a highly versatile and atom-economical alternative to novel methods for the synthesis of various unsymmetrical diarylpyrroles and diarylpyridines under manageable conditions.