Wenna Ge, Fusheng Zhang,* Dongdong Wang, Quanmao Wei, Qiongya Li, Zhixin Feng,Shile Feng, Xingya Xue, Guangyan Qing,* and Yahua Liu*

Small 2022, 18, 2107105

Cellulose nanocrystals (CNCs)–derived photonic materials have confirmed great potential in producing renewable optical and engineering areas. However, it remains challenging to simultaneously possess toughness, strength, and multiple responses for developing high-performance sensors, intelligent coatings, flexible textiles, and multifunctional devices. Herein, the authors report a facile and robust strategy that poly(ethylene glycol) dimethacrylate (PEGDMA) can be converged into the chiral nematic structure of CNCs by ultraviolet-triggered free radical polymerization in an N,N-dimethylformamide solvent system. The resulting CNC–poly(PEGDMA) composite exhibits impressive strength (42 MPa), stretchability (104%), toughness (31 MJ m−3), and solvent resistance. Notably, it preserves vivid optical iridescence, displaying stretchable variation from red, yellow, to green responding to the applied mechanical stimuli. More interestingly, upon exposure to spraying moisture, it executes sensitive actuation (4.6° s−1) and multiple complex 3D deformation behaviors, accompanied by synergistic iridescent appearances. Due to its structural anisotropy of CNC with typical left-handedness, the actuation shows the capability to generate a high probability (63%) of right-handed helical shapes, mimicking a coiled tendril. The authors envision that this versatile system with sustainability, robustness, mechanochromism, and specific actuating ability will open a sustainable avenue in mechanical sensors, stretchable optics, intelligent actuators, and soft robots.