Some Schiff base compounds with aromatic substituted groups and their Cu-complexes have been designed and synthesized from the reaction of aromatic amines with salicylaldehyde. It has been found that depending on the molecular structures and substituted groups, the formed Schiff base compounds showed different properties, indicating distinct regulation of molecular design. UV and IR data confirmed commonly the formation of Schiff base and coordination with Cu(II) ions, as well as aromatic segment in molecular structures. In addition, the process of ex situ coordination seemed to change differently along with adding time, which could be ascribable to the presence of distinct substituted group and change of reaction activity. The spectral difference is mainly attributed to molecular structures, formation of Schiff base group and different substituted groups. The present results have showed that the special properties of Schiff base compounds could be turned by modifying molecular structures and substituted groups, which show potential application in fields of functional material fields such as liquid crystal and catalysts.