Many types of photoreactive polymers have been investigated to regulate their molecularly orientated structures for polarization-controlled optical and display applications. Herein, we demonstrate the axis-selective photoreaction of thin films and their molecular reorientation behaviors using four types liquid crystalline poly(meth)acrylates with phenyl benzoate side groups and linearly polarized (LP) 248 nm light. These simple liquid crystalline polymers (LCPs) exhibit sufficient photoinduced molecular reorientations. Photoinduced molecular reorientation based on an axis-selective photo-Fries rearrangement is simultaneously generated with an in-plane order parameter (S) up to 0.33 when the irradiation temperature is in the lower part of the LC temperature range of the material, but multidomain formation of the mesogenic groups inhibits reorientation. To prevent thermally generated multidomain formation, an axis selective photoreaction of an amorphous film followed by thermally generated self-organization processes effectively induce molecular reorientation with S up to 0.71 and birefringence (Delta n) similar to 0.16