Ferrocene and its derivatives are commonly used electrochemically responsive materials. Ferrocene derivatives have attracted much attention due to their high chemical stability, characteristic electrochemical response and high liquid crystallinity. Azobenzene and its derivatives are important light responsive materials and possess outstanding photochemical properties due to the presence of an azo bond which can isomerize reversibly between trans- and cis-forms under different illumination conditions. These kinds of compounds have been designed for information storage devices, molecular switches, molecular devices and so on. By combining a ferrocene group with an azobenzene group, novel functional materials with outstanding properties of both ferrocene and azobenzene can be obtained. These novel functional materials can be used for wide range of applications like high density information storage, ion recognition, DNA detection, etc. This review summarizes recent progress in ferrocene- and azobenzene-based photoelectric responsive materials, including their synthesis, properties and applications.