Photoinduced orientation of a new photo-cross-linkable liquid crystalline polymer film comprising a 4-methoxycinnamoyloxy group connected with a tolane moiety (PMCT6M) is presented. High molecular reorientation order with a birefringence value of 0.27 is achieved by exposing the film to linearly polarized ultraviolet light and subsequent annealing. The required degree of the photoreaction for the effective reorientation is 2–5 mol %. Small amount of photo-cross-linked mesogenic groups controls the thermal enhancement of the molecular reorientation.