Ice‐templating, also known as directional freezing or freeze‐casting, features the tunability of microstructure, the wide applicability of functional nanomaterials, and the fabrication of multiscale well‐controlled biomimetic materials. Recently, integrating ice‐templating with other materials’ processing technologies (such as, spraying, spinning, filtration, and hydrothermal), it has been investigated to tailor pore morphology of scaffolds for emerging applications. Such integration endows materials with various structures (cellular, dendritic, and lamellar) and dimensions (0D, 1D, 2D, and 3D), which opens up a new avenue for improving material properties and developing new materials. Herein, this review probes into the relationship of integrative ice frozen assembly with structure and describes the fundamental principles and synthesis strategies for preparing multi‐scale materials with complex biomimetic structures via ice‐templating. Focusing on ice crystal nucleation and growth, it summarizes the performance of ice‐templating in constructing pore geometries. Additionally, the review analyzes in depth the correlation between microstructure and macromorphology of final scaffolds, highlighting the application of integrative ice frozen assembly in electrochemical energy storage and conversion, and prospects for future research directions for this field.