Additive manufacturing (AM) has gained significant attention due to its ability to drive technological development as a sustainable, flexible, and customizable manufacturing scheme. Among the various AM techniques, direct ink writing (DIW) has emerged as the most versatile 3D printing technique for the broadest range of materials. DIW allows printing of practically any material, as long as the precursor ink can be engineered to demonstrate appropriate rheological behavior. This technique acts as a unique pathway to introduce design freedom, multifunctionality, and stability simultaneously into its printed structures. Here, a comprehensive review of DIW of complex 3D structures from various materials, including polymers, ceramics, glass, cement, graphene, metals, and their combinations through multimaterial printing is presented. The review begins with an overview of the fundamentals of ink rheology, followed by an in‐depth discussion of the various methods to tailor the ink for DIW of different classes of materials. Then, the diverse applications of DIW ranging from electronics to food to biomedical industries are discussed. Finally, the current challenges and limitations of this technique are highlighted, followed by its prospects as a guideline toward possible futuristic innovations.

Extrusion-based additive manufacturing (AM) enables the fabrication of three-dimensional (3D) structures with intricate cellular architectures where the material is selectively dispensed through a nozzle or orifice in a layer-by-layer fashion at the meso- and micro-scale. Polymers and their composites are one of the most widely used materials in modern industries and are of great interest in the field of AM due to their vast potential for various applications, especially for the medical, military, aerospace, and automotive industries. Because architected polymer-based structures impart remarkably improved material properties such as low density and high mechanical performance compared to their bulk counterparts, this review focuses particularly on the development of such objects by extrusion-based AM intended for structural applications. This review introduces the extrusion-based AM techniques followed by a discussion on the wide variety of materials used for extrusion printing, various architected structures, and their mechanical properties. Notable advances in newly developed polymer and composite materials and their potential applications are discussed in detail and summarized. Finally, perspectives and insights into future research of extrusion-based AM on developing high-performance ultra-light materials using polymers and their composite materials are discussed.