Amphiphilic molecules, comprising hydrophobic and hydrophilic moieties and the intrinsic propensity to self-assemble in aqueous environment, sustain a fascinating spectrum of structures and functions ranging from biological membranes to ordinary soap. Facing the challenge to design responsive, adaptive, and out-of-equilibrium systems in water, the incorporation of photoresponsive motifs in amphiphilic molecular structures offers ample opportunity to design supramolecular systems that enables functional responses in water in a non-invasive way using light. Here, we discuss the design of photoresponsive molecular amphiphiles, their self-assembled structures in aqueous media and at air–water interfaces, and various approaches to arrive at adap...