A number of new acridino[4,3- c]acridinedione derivatives have been synthesized for the first time by condensation of N, N-bis(arylmethylidene)naphthalene-1,5-diamines with cyclic 1,3-diketones (cyclohexane-1,3-dione and dimedone). The product structure has been determined by two-dimensional NMR spectroscopy, and a probable reaction mechanism has been proposed.