The preparation of phthalimides cross-conjugated with an azulene ring was established by a one-pot Diels–Alder reaction of the corresponding 2-aminofuran derivatives with several maleimides, without the isolation of the intermediately formed [4 + 2] cycloadducts. The structure, optical and electrochemical properties of the novel phthalimide derivatives were clarified by single-crystal X-ray analysis, UV/Vis and fluorescence spectra, spectroelectrochemistry and voltammetry experiments, and theoretical calculations. These results indicated that the substituents on the azulene ring greatly affect the optical and electrochemical properties of the molecules.