Abstract: The photochromism of a new star-like liquid crystal that was written by Si(AZO)4 centered by Si and containing four butoxyazobenzene mesogens in its periphery was described. The quantum yield, photoisomerization and photo back-isomerization of Si(AZO)4 in CHCl3 and THF are studied by UV/Vis absorption spectra. The results indicate that the photochromism and photo back-isomerization of Si(AZO)4 in CHCl3 and THF were in accordance with the first order kinetics. The photochromism and photo back-isomerization rate constants are 10-1 s-1, which are 107 times larger than that of side-chain liquid crystalline polymers containing the same azobenzene moieties. These results indicate that the star-like structure does not significantly affect the photoisomerization activity of the azobenzene mesogen in its periphery. The kt/kc of Si(AZO)4 is less than that of azobenzene mesogen which shows that the Si(AZO)4 has better photo-reversibility. So the star-like liquid crystal has potential applications and will become a new type photocontrolable switch and information functional material.