Hollow multishelled structure (HoMS), a promising and complex multifunctional structural system, features at least two shells that are separated by internal voids. The unique structure endows it with numerous advantages including low density, high loading capacity, large specific surface area, facilitated mass transport, and multiple spatial confinement effect. In the past twenty years, benefiting from the booming development of synthesis methods, various HoMS materials have been prepared and show promising applications in diverse areas. HoMS has gradually developed into one of the frontiers of materials and chemistry science, attracting extensive attention from many scientists. In this review, the synthesis chemistry of HoMS and its diverse compositions and structures are systematically introduced, the unique properties of “temporal-spatial ordering” and “dynamic smart behavior” of HoMS are highlighted, and the applications of HoMS in energy storage, catalysis, electromagnetic wave absorption, drug delivery and sensor are fully shown. We hope to reveal the intrinsic relationship between the precise synthesis of HoMS and its tunable composition and structural features. We hope the exploration of frontier scientific concepts and phenomena in HoMS research can provide inspiration for its future direction, and promote the flourishing progress of HoMS.

中空多壳结构（HoMS）是一种有前途且复杂的多功能结构体系，具有至少两个由内部空隙分隔的壳。独特的结构赋予其密度低、负载能力高、比表面积大、便于传质、多重空间限域效应等诸多优点。在过去的二十年里，受益于合成方法的蓬勃发展，各种HoMS材料被制备出来并在不同领域显示出广阔的应用前景。 HoMS已逐渐发展成为材料和化学科学的前沿领域之一，引起了众多科学家的广泛关注。本文系统介绍了HoMS的合成化学及其多样化的组成和结构，重点介绍了HoMS的“时空有序”和“动态智能行为”的独特性质，以及HoMS在能源存储、催化等方面的应用。 ，电磁波吸收、药物输送和传感器都得到了充分的展现。我们希望揭示HoMS的精确合成与其可调组成和结构特征之间的内在关系。我们希望HoMS研究中对前沿科学概念和现象的探索能够为其未来的发展方向提供启发，推动HoMS的蓬勃发展。