A reliable method for preparing polysubstituted pyrroles from conjugated iminohexatrienes has been discovered. Ru(0)-catalyzed cross-dimerization of iminoalkyne with conjugated dienes provides a series of conjugated iminohexatrienes. Subsequent treatment with a catalytic amount of acetic acid (7 mol %) leads to an unexpected cyclization yielding 2-alkenylpyrroles. The overall reaction can be considered as a formal (4 + 1) annulation that involves the formation of a conjugated iminohexatriene followed by an intramolecular aza-Michael-type 5-exo-trig cyclization and subsequent proton migration.