A new series of 3-(furan-2-yl) dibenzo-diazepin-1-one derivatives were synthesized by condensation of 5-(furan-2-yl)-1,3-cyclohexanedione, o-phenylenediamine, and aromatic aldehydes, in which in some of them existed two very close isomer compounds. All the compounds were characterized by IR, MS, 1 H NMR, and elemental analysis. Also presented were the crystal structures of 3a, 3b and 3e, which were obtained and determined by X-ray single-crystal diffraction.