Photoactuators based on liquid crystal elastomers or networks are smart materials that show photoinduced motions. However, their crosslinked networks make their repair or reprocessing difficult. Here, a healable and reprocessable photoactuator is fabricated using entangled high‐molecular‐weight azobenzene‐containing polymers (azopolymers) that are non‐crosslinked. A series of linear liquid crystal azopolymers with different molecular weights are synthesized. The low‐molecular‐weight azopolymers (5–53 kg mol⁻¹) cannot form freestanding photoactuators because their polymer chains lack entanglements, which makes them hard and brittle. In contrast, flexible and stretchable actuators are fabricated using high‐molecular‐weight azopolymers (80–100 kg mol⁻¹) that exhibit good processability because of the polymer chain entanglements. The azopolymer photoactuators show photoinduced bending based on photoinduced trans–cis isomerization of the azopolymers on the irradiated side. The experiments show not only photoinduced phase transitions or changes in the order parameters but also photoinduced solid‐to‐liquid transition of the azopolymers resulting in shape changes and mechanical responses. Thus, photoinduced solid‐to‐liquid transition is a new mechanism for the design of photoactuators. Moreover, the azopolymer photoactuators are healable and reprocessable via solution processing or light irradiation. Healability and reprocessability prolong lifetimes of photoactuators are important for materials reusage and recycling, and represent a new strategy for the preparation of smart materials.

This study proposes a simple method to fabricate a magnetic self-healing poly(vinyl alcohol) (ms-PVA) composite hydrogel. The obtained ms-PVA hydrogel was characterized by vibrating sample magnetometery and transmission electron microscopy. The self-healing property was investigated using a rheometer and tensile strength tests. Results showed that the ms-PVA hydrogel exhibited an excellent self-healing property and controllable magnetic intensity by adjusting the Fe₃O₄ particle content. The added Fe₃O₄ particles did not participate in hydrogen bond interactions but did cause the magnetic properties of the hydrogel. The hydrogel showed the best self-healing performance when the amount of Fe₃O₄ particles was 5 wt% (based on ms-PVA). The ms-PVA composite hydrogel presents a new application of the PVA hydrogel given its facile fabrication process and excellent performance.