A short and simple synthesis of chromeno[4,3-b]benzo[f]quinoline and quinolino[4,3-b]benzo[f]quinoline derivatives were accomplished in high yields via the reaction of N-benzilidenenaphthalen-2-amine and 4-hydroxycoumarin or 4-hydroxyquinolin-2-one in aqueous media catalyzed by TEBAC. The structures were established by spectroscopic data and further confirmed by X-ray diffraction analysis.