The effect of ultraviolet photoirradiation on the azo-bent-core liquid crystal electronic structure and the optical properties was studied by ultraviolet-visible spectrophotometry observation and electronic structure calculation. The optical absorption spectrum showed that two optical absorption peaks appear at about 360 nm and 275 nm which originated from electronic transitions of azo-chromophores indicated by electronic calculation. The result showed that nitrogen double bonds in the azo-containing liquid crystal can be broken when it is exposed to 365 nm irradiation which caused the absorption, decreasing rapidly at 360 nm and increasing accordingly at 275 nm, and which indicated the occurring of photo-dissociation.