Photoreorientation processes in photochromic LCP’s are dependent on the supramolecular order. The efficiency is much higher in films of low order, which have been obtained by a suitable preparation or by an intermediate photochemical decoupling. On the other hand, a photochemically induced order in an initially isotropic film acts as initializing force, governing the direction of thermotropic self-organization. The combination of both ordering principles causes a significant amplification of the light-induced optical anisotropy.