The effects of molecular environments on photoisomerization of an azobenzene group were investigated using in-situ UV/Vis spectroscopy and optical anisotropy measurement technique. The reversible and repeatable photoisomerization reactions of azobenzene were observed by irradiating the film containing 4-hydroxyazobenzene and by measuring absorption intensities of the characteristic bands of trans and cis isomers simultaneously. When the self-assembled monolayer with azobenzene groups was used as an alignment layer for a liquid crystal cell, the homeotropic alignment was induced due to their compact packing structures of azobenzene groups along the vertical direction of the substrate. By irradiating UV light on this cell, the trans-azobenzene groups change to cis-isomers through the photoisomerization and then resulting in the planar alignment of liquid crystal molecules.