Hierarchical self-assembly and crystallization with long-range ordered spatial arrangement is ubiquitous in nature and plays an essential role in the regulation of structures and biological functions. Inspired by the multiscale hierarchical structures in biology, tremendous efforts have been devoted to the understanding of hierarchical self-assembly and crystallization of biomolecules such as peptides and amino acids. Understanding the fundamental mechanisms underlying the construction and organization of multiscale architectures is crucial for the design and fabrication of complex functional systems with long-range alignment of molecules. This Review summarizes the typical examples for hierarchically oriented organization of peptide self-assembly and discusses the thermodynamic and kinetic mechanisms that are responsible for this specific hierarchical organization. Most importantly, we propose the concept of hierarchically oriented organization for self-assembling peptide crystals, distinct from the traditional growth mechanism of supramolecular polymerization and crystallization based on the Ostwald ripening rule. Finally, we assess critical challenges and highlight future directions towards the mechanistic understanding and versatile application of the hierarchically oriented organization mechanism.

具有远距离有序空间排列的分层自组装和结晶在自然界是普遍存在的，并且在结构和生物学功能的调节中起着至关重要的作用。受生物学中多尺度分层结构的启发，人们付出了巨大的努力来理解诸如肽和氨基酸之类的生物分子的分层自组装和结晶。了解多尺度体系结构的构建和组织的基本机制对于分子长距离排列的复杂功能系统的设计和制造至关重要。这篇综述总结了肽自组装的层次定向组织的典型例子，并讨论了负责这种特定层次组织的热力学和动力学机理。最重要的是，我们提出了自组装肽晶体的分层定向组织概念，这与基于奥斯特瓦尔德成熟规则的超分子聚合和结晶的传统生长机制不同。最后，我们评估了关键挑战，并突出了对面向层次的组织机制的机械理解和广泛应用的未来方向。不同于传统的基于奥斯特瓦尔德（Ostwald）成熟规律的超分子聚合和结晶生长机理。最后，我们评估了关键挑战，并突出了对面向层次的组织机制的机械理解和广泛应用的未来方向。不同于传统的基于奥斯特瓦尔德（Ostwald）成熟规律的超分子聚合和结晶生长机理。最后，我们评估了关键挑战，并突出了对面向层次的组织机制的机械理解和广泛应用的未来方向。