The photoinduced reorientation of the side-chain mesogens in nematic liquid crystalline (LC) polymer thin films triggered by the axis-selective photo-Fries rearrangements of side-chain phenyl benzoate moieties is studied to understand the regulation of the anisotropic nanostructures supported by LC polymers. The influence of the substrate surface in anchoring the side-chain mesogens near the interfaces is examined by comparing the reorientation of 30- and 120-nm-thick films. Irradiation with linearly polarized ultraviolet (UV) light and subsequent annealing causes the side-chain mesogen reorientation to align perpendicular to the electric field of the incident UV light. The inplane order in the 30-nm-thick films is lower than that in the 120-nm ones. On the other hand, the annealing period required for mesogen alignment is independent of the film thickness. It is suggested that the substrate surfaces anchor the LC mesogens to fix their orientation, rather than slowing down the reorientational motion. In addition, it is demonstrated that small LC molecules miscible with the nematic LC polymer enhance photoinduced reorientation through cooperative molecular interaction with the side-chain mesogens, remarkably accelerating the orientation and improving the inplane order of the unidirectionally aligned mesogens.