Four-dimensional printing allows for the transformation capabilities of 3D-printed architectures over time, altering their shape, properties, or function when exposed to external stimuli. This interdisciplinary technology endows the 3D architectures with unique functionalities, which has generated excitement in diverse research fields, such as soft robotics, biomimetics, biomedical devices, and sensors. Understanding the selection of the material, architectural designs, and employed stimuli is crucial to unlocking the potential of smart customization with 4D printing. This review summarizes recent significant developments in 4D printing and establishes links between smart materials, 3D printing techniques, programmable structures, diversiform stimulus, and new functionalities for multidisciplinary applications. We start by introducing the advanced features of 4D printing and the key technological roadmap for its implementation. We then place considerable emphasis on printable smart materials and structural designs, as well as general approaches to designing programmable structures. We also review stimulus designs in smart materials and their associated stimulus-responsive mechanisms. Finally, we discuss new functionalities of 4D printing for potential applications and further development directions.
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