Structural complexity in nature emerges from simple building blocks, yielding ro-bust and multifunctional materials. In response to the growing demand for pro-grammable, time-sensitive materials, metal-organic frameworks (MOFs) have emerged as ideal platforms for engineering complexity across multiple scales and environments. Their modularity allows the incorporation of multivariate metal nodes and organic linkers based on their topology, creating tailored pore environments and spatially varied functionalities. This review categorizes MOFs into three strategic approaches to structural complexity: metal node de-fect engineering, multivariate linker design, and hierarchical pore engineering. These approaches are highlighted for their broad application potential and offer valuable insights for the future design of complex, functional materials.