Owing to the developments in laser processing technology and liquid crystal alignment technology, a novel compartmentalized out-of-plane alignment technology of liquid crystals based on femtosecond laser direct writing is introduced. Femtosecond multiphoton polymerization based laser direct writing is used to prepare microstructures comprising polymeric ribbons. The liquid crystal cells are fabricated by filling different kinds of liquid crystals that can then function as an electro-optical switch, a magneto-optical switch, and light field control. The surface relief grating structures are distributed on the sidewalls of each polymer ribbon, which make it possible for liquid crystal orientation within the polymeric ribbon channel. The technology can realize the physical isolation of liquid crystals in different regions and complete phase separation of liquid crystals and polymers. The proposed technology is fast and simple, which has great application value in tunable diffraction gratings, special light field generation, and light field control in photonic crystals.