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 contraction, and self‐catalytic pyrolysis. By analyzing and discussing 14 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. Recent developments of controlled synthesis of hollow‐structured functional materials by using metal–organic framework as precursors are summarized, along with their promising applications in electrochemical energy storage and conversion.