Amphiphilic molecules, are composed of hydrophobic and hydrophilic parts and the intrinsic tendence to assemble in aqueous conditions, producing numerous supramolecular assembled structures and functional systems. Some of the recent challenges in the design of adaptive, responsive, far-from-equilibrium functional systems in aqueous environments, the proper design of photo-controlled moieties in intrinsic charged amphiphilic molecular structures offers fruitful opportunities to create supramolecular assembly systems, based on electrostatic interaction, with response to light in aqueous environment. In this chapter, we discuss the design strategy of photo-controlled molecular amphiphiles, the supramolecular assembled structures in aqueous environment and at air–water interfaces, as well as different strategies for producing dynamic functions in both isotropic and anisotropic supramolecular assembled materials. The motions at air–water interface, foam formation, reversible supramolecular assembly at nanometer length-scale, and life-like artificial muscle function are discussed. Manipulating the molecular structural design, supramolecular assembling conditions, and external stimulation, the photo-controlled molecular amphiphiles open directions toward applications ranging from controlled bio-target delivery to soft robotic.