When a nematic liquid crystal is doped with a large amount of a liquid crystalline azobenzene compound (15 wt %), the photoisomerization of azobenzene under UV and visible light irradiation can give rise to reversible and interconvertible photochemical phase transition and photochemical phase separation. Both normal and reverse modes of photocontrolled switching of transmittance through crossed polarizers can be realized with the same mixture of liquid crystal/azobenzene dopant.