A series of azobenzene-containing fluorescent complexes with stilbene fluorescent unit were prepared based on the ionic self assembly approach. The incorporation of the stilbene unit did not change the lamellar structure of the azobenzene-containing complex. Under pulsed laser irradiation, the azobenzene group oriented in the direction perpendicular to the laser polarization, and as a result, the fluorescent stilbene unit was cooperatively oriented following the direction of azobenzene group orientation. This oriented complex films presented anisotropic emission of fluorescence, and the anisotropic ratio of fluorescence increases with the increase of the content of azobenzene unit in the complex.