With the rapid development of the 3D printing technique, the concept of 4D has emerged, defining time as the fourth dimension. This concept allows for changes in the appearance, function, or other properties of 3D printed objects in response to certain controlled external stimuli over time. In this work, a new photocomposite containing fluorescein based is designed on an interpenetrating polymer network (IPN) system, this system can be generated by the simultaneous photopolymerization of acrylate and epoxide monomers under visible LED@405 nm irradiation. Unexpectedly, combining the reversible fluorometric turn‐on property of fluorescein and the deformation of the IPN in the presence of water, the 3D flower structure printed from this photocomposite would demonstrate a novel dual responsive behavior with both fluorescence and shape changes when it is exposed to water for a short time. This work would present a novel functional photocomposite material and also expand the application prospect of 4D printing. [ABSTRACT FROM AUTHOR]