The oxidative demethylation of ortho-dimethoxyacridone with ceric ammonium nitrate (CAN) regioselectively furnished an ortho-quinone leaving a methoxyl group unreacted, which further condensed with aromatic ortho-diamines to afford angularly fused π-extended acridone derivatives. Crystallographic analysis reveals the distinct manner of molecular packing in the crystals according to the dimension of π-extension. The benzene at the turning point possesses a shorter outer bond and a longer inner bond, which affects molecular conjugation and results in weakened aromaticity.