LAUSR

Temperature‐responsive microgels find widespread applications as soft materials for designing actuators in microfluidic systems, as carriers for drug delivery or catalysts, as functional coatings, and as adaptable sensors. The key property is their volume phase transition temperature, which allows for thermally induced reversible swelling/deswelling. It is determined by the gel's chemical structure as well as network topology and cannot be varied easily within one system. Here a paradigm change of this notion by facilitating a light‐triggered reversible switching of the microgel volume in the range between 32 and 82 °C is suggested. Photo‐sensitivity is introduced by photosensitive azobenzene containing surfactant, which forms a complex with microgels consisting of poly(N‐isopropylacrylamide‐co‐acrylic acid) (PNIPAM‐AAc) chains when assuming a hydrophobic trans‐state, and prefers to leave the gel matrix in its cis‐state. Using a similar strategy, it is demonstrated that at a fixed temperature, for example, 37 °C, one can reversibly change the microgel radius by a factor of 3 (7–21 µm) by irradiating either with UV (collapsed state) or green light (swollen state). It is envisaged that the possibility to deploy a swift external means of adapting the swelling behavior of microgels may impact and redefine the latter's application across all fields.