The FeCl3-promoted ring size-controlled oxidative activation of o-alkynylanilines opens up a complementary appealing protocol for poly-N-heterocycle synthesis. When electron-poor π-alkyne iron species combine with cyclic enamines obtained from cyclohexanone and β-tetralone, they undergo a regioselective 6-exo-dig cyclization to afford the corresponding dibenzo[b,j][1,10]phenanthrolines and 12-benzoylated dihydrobenzo[a]acridine skeletons. Later, these acridine motifs become completely unsaturated due to dehydrogenative aromatization via the aza-allyl oxidation intermediate. We obtained all quaternary carbon centre pseudoindoxyls through the Mannich-type alkylation of 2,3-dihydro-1H-inden-1-one with cyclic ketimines generated from the in situ intramolecular nucleophilic cyclization of o-alkynylanilines.