Photosensitive materials for photoalignment of liquid crystals (LCs) and photoinduced molecular reorientation are described, especially focusing on azobenzene-containing materials and photocrosslinkable polymers. All the materials generate photoinduced optical anisotropy by means of linearly polarized (LP) light exposure. The large optical anisotropy is induced when the axis-selective photoreaction is accompanied by molecular reorientation.