We investigated effect of annealing after rubbing by grazing incidence X-ray diffraction, since annealing process is performed in the actual process of liquid crystal display (LCD) fabrication. It was found that rubbed surface polymers were highly crystallized by annealing at 250°C after rubbing, and that the crystallization of surface polymers by annealing occurred in the aligned polymer region induced by rubbing. Crystallization of surface polymers by annealing increasingly occurred as increasing of rubbing strength. Thus, it is considered that annealing process after rubbing should also play an important role to control liquid crystal alignment in LCD.