Some functional azobenzene derivatives with aromatic substituted groups have been synthesized and their photoisomerization have also been investigated. It has been found that depending on different substituted groups, such as phenyl or naphthyl segments, the formed azobenzene derivatives showed different properties, indicating distinct regulation of molecular skeletons. Spectral data confirmed commonly the characteristic absorption of substituted groups and aromatic segments in molecular structures. In addition, the photoisomerization of all compounds in solution can show trans-to-cis photoisomerization by UV light irradiation, and demonstrate distinct isomerization ratio depending on effect of different substituted headgroups. The difference is mainly attributed to the aromatic substituted headgroups and methyl group in molecular structure. The present results have showed that the special properties of azobenzene derivatives could be effectively turned by modifying molecular structures of objective compounds with proper substituted groups, which show potential application in sensor and functional material field.