A new photo-cross-linkable liquid crystalline polymer (PLCP) comprised 4-methoxycinnamoyloxy groups connected with a bistolane side group was synthesized to investigate thermally enhanced photoinduced molecular reorientation of a thin film with linearly polarized (LP) 365 nm light exposure. Due to the axis-selective photoreaction of the cinnamate groups followed by the thermally induced self-organization, large molecular reorientation parallel to the polarization of LPUV light (S > 0.6) and large birefringence at the non-resonance region (Delta n = 0.34 at 632.8 nm) were obtained. The obtained An value is the largest among transparent PLCPs in the visible region. The influence of the degree of photoreaction and the annealing temperature on the thermally enhanced molecular reorientation behavior was explored in detail. Finally, for an application of thin optical devices using the PLCP films, pure polarization holographic gratings with large birefringence, which showed periodic molecularly oriented structure, were fabricated using a 325 nm He-Cd laser in various polarization modes and characterized their optical properties. (C) 2010 Elsevier Ltd. All rights reserved.