Photoreactive olefinic species are incorporated into a metal–organic framework (MOF), [Zn(bdc)(3‐F‐spy)] (1). Single crystals of 1 are shown to undergo three types of photomechanical macroscopic deformation upon illumination by UV light. To demonstrate the practical potential of this system, the inclusion of 1 in a PVA (polyvinyl alcohol) composite membrane, by exploiting hydrogen‐bonding interactions, is presented. Using this composite membrane, the amplification of mechanical stress to achieve macroscopic actuation behavior is demonstrated. These results pave the way for the generation of MOF‐based soft photoactuators that produce clearly defined mechanical responses upon irradiation with light. Such systems are anticipated to have considerable potential in photomechanical energy harvesting and conversion systems.