We describe thermally enhanced molecular reorientation of photo-crosslinkable methacrylate copolymer liquid crystal (CPLC) films with a photoreactive 6-[4-(2-cinnamoyloxyethoxy)biphenyloxy]hexyl side group and a photoinactive n-(4-cyanobiphenyloxy)alkyl (nCB, n = 5 or 6) side group. The alignment of the mesogenic groups was induced by irradiation with a linearly polarized ultraviolet (LPUV) light and subsequent annealing at different heating rates. The orientational behavior was investigated by polarized UV and FT-IR spectroscopy. For a film of copolymer P1 (n = 6), both mesogenic groups aligned homogeneously in a direction parallel to the electric vector (E) of the incident LPUV light regardless of the annealing conditions. On the other hand, the heating rate highly influenced the orientational behavior of a film of P2 (n = 5). The out-of-plane alignment of mesogenic side groups was observed when the heating rate after the LPUV light exposure was 90°C/min, while in-plane alignment was more prevalent in the mesogenic groups for the slow heating rate. Tilt angle control of the alignment direction was feasible by the use of oblique LPUV light irradiation. In addition, the inclination angle of the mesogenic groups for the P2 film could be regulated at the same irradiation angle by changing the heating rate.