Preparation of interfacial structures by molecular self-assembly has been actively studied for many years. Well-defined modified interfaces can be used to study fundamental interfacial properties, or they can be used in different practical applications. To broaden the utility of interfaces prepared by molecular self-assembly, monolayers containing terminal functionality are frequently used. These interfaces have structural and physical properties that can be controlled by both the identity of the functionalization as well as the ensemble structure of the modified interface. This suggests that the chemical and physical properties of an interface can be designed and/or controlled to some extent by altering the structural details of the molecules used to generate the interface.