HighlightsThe recent development and implementation of metal–organic frameworks (MOFs) and MOF-based materials in electrochemical water applications are reviewed.The critical factors that affect the performances of MOFs in the electrochemical reactions, sensing, and separations are highlighted.Advanced tools, such as pair distribution function analysis, are playing critical roles in unraveling the functioning mechanisms, including local structures and nanoconfined interactions.AbstractMetal–organic frameworks (MOFs), a family of highly porous materials possessing huge surface areas and feasible chemical tunability, are emerging as critical functional materials to solve the growing challenges associated with energy–water systems, such as water scarcity issues. In this contribution, the roles of MOFs are highlighted in electrochemical-based water applications (i.e., reactions, sensing, and separations), where MOF-based functional materials exhibit outstanding performances in detecting/removing pollutants, recovering resources, and harvesting energies from different water sources. Compared with the pristine MOFs, the efficiency and/or selectivity can be further enhanced via rational structural modulation of MOFs (e.g., partial metal substitution) or integration of MOFs with other functional materials (e.g., metal clusters and reduced graphene oxide). Several key factors/properties that affect the performances of MOF-based materials are also reviewed, including electronic structures, nanoconfined effects, stability, conductivity, and atomic structures. The advancement in the fundamental understanding of these key factors is expected to shed light on the functioning mechanisms of MOFs (e.g., charge transfer pathways and guest–host interactions), which will subsequently accelerate the integration of precisely designed MOFs into electrochemical architectures to achieve highly effective water remediation with optimized selectivity and long-term stability.