We report a new strategy, the directional peeling of a rigiflex mold with a nanostructure, to overcome several problems with general patterning techniques for liquid‐crystal (LC) alignment. These include difficulty in generating the pretilt angle and in controlling the LC rising‐up direction, formation of local domains, and weak optical properties. The directional peeling of the rigiflex mold results in pretilt‐angle formation and controls the LC rising‐up direction. In addition, a nanostructure with small spacing aligns the LC with a high order parameter because of a strong confinement effect and suppresses diffraction due to its small spacing. Eventually, the nanostructure achieves improvements in the optical properties. In summary, while recent patterning techniques for LC alignment only solve one problem, the directional peeling of the rigiflex mold with a nanostructure simultaneously overcomes several problems with LC alignment and optical properties.