Two functional azobenzene derivatives with alkyl chains and different substituted groups have been synthesized and their photoisomerization have also been investigated. It has been found that depending on the alkyl chain and different substituted groups, the formed azobenzene derivatives showed different properties, indicating distinct regulation of molecular skeletons. UV and IR data confirmed commonly the characteristic absorption of alkyl chain and aromatic segments in molecular structures. Thermal analysis demonstrated that the structural influence of both compounds in different temperature ranges. The difference of thermal stability is mainly attributed to the formation of Schiff base group and different substituent groups in molecular structure. The photoisomerization of these compounds both in solution and in cast film can undergo trans-to-cis isomerization by UV light irradiation, depending on different substituted groups. The present results have demonstrated that the special properties of azobenzene derivatives can be effectively turned by modifying molecular structures of objective compounds with proper substituted groups, which show potential application in functional material field.