Amplification of molecular motions into the macroscopic world has great potential in the development of smart materials. Demonstrated here is an approach that integrates mechanically interlocked molecules into complex three‐dimensional (3D) architectures by direct‐write 3D printing. The design and synthesis of polypseudorotaxane hydrogels, which are composed of α‐cyclodextrins and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO‐PPO‐PEO) triblock copolymers, and their subsequent fabrication into polyrotaxane‐based lattice cubes by 3D printing followed by post‐printing polymerization are reported. By switching the motion of the α‐cyclodextrin rings between random shuttling and stationary states through solvent exchange, the polyrotaxane monolith not only exhibits macroscopic shape‐memory properties but is also capable of converting the chemical energy input into mechanical work by lifting objects against gravity.
In motion: A polyrotaxane monolith has been fabricated using a direct‐writing 3D printing method. The monolith exhibits reversible shape deformation and recovery capabilities controlled by the cyclodextrin ring motions on the axle of the polyrotaxane. DMSO=dimethylsulfoxide.