Controlling the birefringence of optical films is imperative to fabricate thin birefringent optical devices. Here, new photoalignable liquid crystalline copolymers (PLCPs) with 4formylphneyl benzoate (PA) and cinnamic acid (CA) side groups are synthesized, which attain high photoreactivity and controllability of the orientation direction. Additionally, the exposed films are treated with 2-aminofluorene (AF) for an in situ condensation of PA with AF to form a Schiff base with a high inherent birefringence. Birefringence of the photoaligned film can be controlled up to 0.45 without disturbing the photoinduced orientation structure.