Four-dimensional (4D) printing of biopolymers is an exciting field of research that has emerged over the last decade. It encompasses printing smart polymeric materials that change their geometrical properties, such as shape, size, and volume, as well as mechanical properties, such as stiffness, upon stimulation with an external stimulus. Three-dimensional (3D) structures with exciting properties and functions can be developed with these biomaterials, spanning applications from tissue engineering to drug delivery. Furthermore, 4D printing of biomaterials is an excellent choice for bioprinting as the printed tissues/organs evolve post-printing over time but in a programmed manner. However, there is limited work done in this area. This chapter provides an overview of the process of 4D printing of biopolymers, the state-of-the-art in this area, and innovative examples from recent research work. Moreover, the limitations and challenges are also highlighted. Finally, the future perspective and general direction are provided. © 2023 Elsevier Inc. All rights reserved.