Hollow materials derived from metal-organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow-structured materials. The synthetic strategies of MOF-derived hollow-structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template-mediated assembly, stepped dissolution-regrowth, selective chemical etching, interfacial ion exchange, heterogeneous construction, and self-catalytic pyrolysis. By analyzing and discussing fourteen types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow-structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium-ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.

Herein, we report a novel method for the formation of hollow Prussian blue analogue (CoFe–PBA) nanocubes, using spherical silica particles as sacrificial templates. In the first step, silica cores are coated by a CoFe–PBA shell and then removed by etching with hydrofluoric acid (HF). The cubic shape of CoFe–PBA is well‐retained even after the removal of the silica cores, resulting in the formation of hollow CoFe–PBA cubes. The specific capacity of the hollow CoFe–PBA nanocubes electrodes is about two times higher than that of solid CoFe–PBA nanocubes as storage materials for sodium ions. Such an improvement in the electrochemical properties can be attributed to their hollow internal nanostructure. The hollow architecture can offer a larger interfacial area between the electrolyte and the electrode, leading to an improvement in the electrochemical activity. This strategy can be applied to develop PBAs with hollow interiors for a wide range of applications.