Some functional Schiff base derivatives with azobenzene substituted groups have been designed and synthesized from the reaction of aminoazobenzene with different aromatic aldehydes. It has been found that depending on the size of aromatic groups, the formed Schiff base derivatives showed different properties, indicating distinct regulation of molecular skeletons. UV and IR data confirmed commonly the formation of Schiff base as well as aromatic segment in molecular structures. Thermal analysis showed that the thermal stability of Schiff base molecules with naphthalene segment increased slightly in comparison with other derivatives. The difference of thermal stability is mainly attributed to the formation of Schiff base group and aromatic substituent groups in molecular structure. The present results have demonstrated that the special properties of Schiff base derivatives can be turned by modifying molecular structures of objective compounds with proper substituted groups, which show potential application in functional material field.