Polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) measurement is performed to investigate orientation structures of the near-surface of the reoriented photo-cross-linkable liquid crystalline polymer (PMCB6M) films, which are applicable to liquid crystal (LC) alignment layer. The 3D orientation parameter at the near-surface of the reoriented PMCB6M film is similar to 0.7, which is similar to the results obtained by a polarization absorption spectroscopy that evaluates the reorientation behavior in bulk. Furthermore, more preferable in-plane orientation is observed at the nearest surface of the film, and the phenyl rings in the reoriented mesogenic side groups show slightly perpendicular orientation to the surface normal.