A photochemically tunable structural color material was prepared by infiltration of the polymer liquid crystal (LC) having azo-chromophores in a SiO2 inverse opal structure. The SiO2 inverse opal film infiltrated with the polymer LC reflected a light, which is called a structural color, corresponding to the periodicity as well as the refractive indices of the inverse opal structure. Linearly polarized light irradiation caused the shift of the structural color band to longer wavelength more than 15 nm. This is caused by the formation of uniaxially anistorpic molecular orientation of the polymer LC. The switched state was stable under interior light, and reversible switching of the reflection band can be achieved by the linearly and circularly polarized light irradiation. This photoswitching property will be suitable for various optical materials such as memory, display so on.