A new strategy to tackle the orientation-relaxation of the chromophores was developed and used to prepare a film which was consisted of polymethyl methacrylate (PMMA) and photo-cross-linkable polyurethane oligomer (PU). The PU contained spindle-type chromophore and terminated with methacrylolyl groups as cross-linkable group. The chemical reaction process was characterized by infrared spectroscopy and the structure of reaction products were characterized by NMR spectroscopy. The surface morphology of the films was investigated by atomic force microscopy (AFM) images. The electro-optic (EO) coefficient of the prepared film was measured by using Teng-Man technique. The cross-linked films containing 15 wt% of the chromophore units displayed a high EO coefficient up to 41 pm/V. The 5% weight loss temperature was 228 A degrees C for the film after photo-cross-linking. Compared with the uncross-linked films, their thermal and temporal stability were greatly improved.