TfOH/HFIP cooperative-catalyzed intramolecular [5+1] cyclodimerization reaction of (E)-2-benzoyl-3-(2-(phenylethynyl)phenyl)acrylonitrile has been disclosed. This highly regio- and chemoselective, operationally simple open air, nonanhydrous solvents protocol occurs exclusively under transition-metal-free conditions through the nitrile activation. Notably, this metal-free strategy is compatible with a diverse range of functional group with synthetically useful yields, even on gram scales to assemble a rare class of stacked architectures final products in one pot reaction.