The utilization of intermittent renewable energy sources needs low-cost, reliable energy storage systems in the future. Among various electrochemical energy storage systems, redox flow batteries (RFBs) are promising with merits of independent energy storage and power generation capability, localization flexibility, high efficiency, low scaling-up cost, and excellent long charge/discharge cycle life. RFBs typically use metal ions as reacting species. The most exploited types are all-vanadium RFBs (VRFBs). Here, we discuss the core components for the VRFBs, including the development and application of different types of membranes, electrode materials, and stack system. In addition, we introduce the recent progress in the discovery of novel electrolytes, such as redox-active organic compounds, polymers, and organic/inorganic suspensions. Versatile structures, tunable properties, and abundant resources of organic-based electrolytes make them suitable for cost-effective stationary applications. With the active species in solid form, suspension electrolytes are expected to provide enhanced volumetric energy densities.