Liquid crystalline (LC) telomers have been synthesized and their thermal as well as photochemical properties are reported. The effects of telogen content on the degree of telomerization and molecular weights of the telomers were also studied. The molecular weights of the telomers were found to decrease with an increase in the telogen content in the telomerization. Isotropization temperatures of the telomers from liquid crystalline to isotropic phase were determined as a measure of the stability of the telomers which showed that stability depends on its molecular weight and structure of the telogen. The telomers also showed fast photoresponsive properties due to the disorganization of the uniaxial molecular orientation caused by the trans-cis photoisomerization of the azobenzene groups.