Abstract The Langmuir monolayer of carboxylic methyl ester Gemini surfactants with the azobenzene spacer, referred to as MC m (azo)MC m , was prepared and the π ‐ A isotherms were measured. The result revealed an orientational picture of the azobenzene spacer at the air/water interface. Before irradiation, the planar trans ‐azobenzene group adopted an approximate configuration parallel to the interface and lay on the air/water interface. After UV‐light irradiation, the spacer became the twisted cis ‐one. Because of the location of the polar headgroups at the air/water interface, the two phenyl rings were also forced to take a near‐parallel orientation with the interface to reduce the free energy. As a result, the spacer thin‐layer was "thickened", which caused an elevation in collapse pressure.