Recently, the appeal of Hybrid Energy Storage Systems (HESSs) has been growing in multiple application fields, such as charging stations, grid services, and microgrids. HESSs consist of an integration of two or more single Energy Storage Systems (ESSs) to combine the benefits of each ESS and improve the overall system performance, e.g., efficiency and lifespan. Most recent studies on HESS mainly focus on power management and coupling between the different ESSs without a particular interest in a specific type of ESS. Over the last decades, Redox-Flow Batteries (RFBs) have received significant attention due to their attractive features, especially for stationary storage applications, and hybridization can improve certain characteristics with respect to short-term duration and peak power availability. Presented in this paper is a comprehensive overview of the main concepts of HESSs based on RFBs. Starting with a brief description and a specification of the Key Performance Indicators (KPIs) of common electrochemical storage technologies suitable for hybridization with RFBs, HESS are classified based on battery-oriented and application-oriented KPIs. Furthermore, an optimal coupling architecture of HESS comprising the combination of an RFB and a Supercapacitor (SC) is proposed and evaluated via numerical simulation. Finally, an in-depth study of Energy Management Systems (EMS) is conducted. The general structure of an EMS as well as possible application scenarios are provided to identify commonly used control and optimization parameters. Therefore, the differentiation in system-oriented and application-oriented parameters is applied to literature data. Afterwards, state-of-the-art EMS optimization techniques are discussed. As an optimal EMS is characterized by the prediction of the system’s future behavior and the use of the suitable control technique, a detailed analysis of the previous implemented EMS prediction algorithms and control techniques is carried out. The study summarizes the key aspects and challenges of the electrical hybridization of RFBs and thus gives future perspectives on newly needed optimization and control algorithms for management systems.