Biological materials and organisms possess the fundamental ability to self‐organize, through which different components are assembled from the molecular level up to hierarchical structures with superior mechanical properties and multifunctionalities. These complex composites inspire material scientists to design new engineered materials by integrating multiple ingredients and structures over a wide range. Additive manufacturing, also known as 3D printing, has advantages with respect to fabricating multiscale, and multi‐material structures. The need for multifunctional materials is driving 3D printing techniques toward arbitrary 3D architectures with the next level of complexity. In this paper, we aim to highlight key features of those 3D printing techniques that can produce either multiscale or multimaterial structures, including innovations in printing methods, materials processing approaches, and hardware improvements. Several issues and challenges related to current methods are discussed. Ultimately, we also provide our perspective on how to realize the combination of multiscale and multimaterial capabilities in 3D printing processes and future directions based on emerging research.This article is protected by copyright. All rights reserved