The fast development of Internet of Things and the rapid advent of next‐generation versatile wearable electronics require cost‐effective and highly‐efficient electroactive materials for flexible electrochemical energy storage devices. Among various electroactive materials, binder‐free nanostructured arrays have attracted widespread attention. Featured with growing on a conductive and flexible substrate without using inactive and insulating binders, binder‐free 3D nanoarray electrodes facilitate fast electron/ion transportation and rapid reaction kinetics with more exposed active sites, maintain structure integrity of electrodes even under bending or twisted conditions, readily release generated joule heat during charge/discharge cycles and achieve enhanced gravimetric capacity of the whole device. Binder‐free metal‐organic framework (MOF) nanoarrays and/or MOF‐derived nanoarrays with high surface area and unique porous structure have emerged with great potential in energy storage field and been extensively exploited in recent years. In this review, common substrates used for binder‐free nanoarrays are compared and discussed. Various MOF‐based and MOF‐derived nanoarrays, including metal oxides, sulfides, selenides, nitrides, phosphides and nitrogen‐doped carbons, are surveyed and their electrochemical performance along with their applications in flexible energy storage are analyzed and overviewed. In addition, key technical issues and outlooks on future development of MOF‐based and MOF‐derived nanoarrays toward flexible energy storage are also offered.