4D printing has attracted academic interest in the recent years because it endows static printed structures with dynamic properties with the change of time. The shapes, functionalities, or properties of the 4D printed objects could alter under various stimuli such as heat, light, electric, and magnetic field. Briefly, 4D printing is the development of 3D printing with the fourth dimension of time. Among the fabrication techniques that have been employed for 4D printing, the direct ink writing technique shows superiority due to its open source for various types of materials. Herein, the state‐of‐the‐art achievements about the topic of 4D printing through direct ink writing are summarized. The types of materials, printing strategies, actuated methods, and their potential applications are discussed in detail. To date, most efforts have been devoted to shape‐shifting materials, including shape memory polymers, hydrogels, and liquid crystal elastomers, showing great prospects in areas ranging from the biomedical field to robotics. Finally, the current challenges and outlook toward 4D printing based on direct ink writing are also pointed out to leave open a significant space for future innovation.

Shape memory polymers (SMPs) and their composites (SMPCs) are smart materials that can be stably deformed and then return to their original shape under external stimulation, thus having a memory of their shape. Three-dimensional (3D) printing is an advanced technology for fabricating products using a digital software tool. Four-dimensional (4D) printing is a new generation of additive manufacturing technology that combines shape memory materials and 3D printing technology. Currently, 4D-printed SMPs and SMPCs are gaining considerable research attention and are finding use in various fields, including biomedical science. This review introduces SMPs, SMPCs, and 4D printing technologies, highlighting several special 4D-printed structures. It summarizes the recent research progress of 4D-printed SMPs and SMPCs in various fields, with particular emphasis on biomedical applications. Additionally, it presents an overview of the challenges and development prospects of 4D-printed SMPs and SMPCs and provides a preliminary discussion and useful reference for the research and application of 4D-printed SMPs and SMPCs.

Shape memory polymers (SMPs) have historically attracted attention for their unique stimulation-responsive and variable stiffness and have made notable progress in aerospace, civil industry, and other fields. In particular, epoxy resin (EP) has great potential due to its excellent mechanical properties, fatigue resistance, and radiation resistance. Herein, we focus on the molecular design and network construction of shape memory epoxy resins (SMEPs) to provide opportunities for performance and functional regulation. Multifunctional and high-performance SMEPs are introduced in detail, including multiple SMEPs, two-way SMEPs, outstanding toughness, and temperature resistance. Finally, emerging applications of SMEPs and their composites in aerospace, four-dimensional printing, and self-healing are demonstrated. Based on this, we point out the challenges ahead and how SMEPs can integrate performance and versatility to meet the needs of technological development.