Hybrid capacitors are emerging because of their ability to store large amounts of energy, cycle through charges quickly, and maintain stability even in harsh environments or at extreme temperatures. Hybrid capacitors with monovalent cations such as Li⁺, Na⁺, and K⁺ have been extensively studied. However, the flammable nature of organic electrolytes and the reactive alkali metallic electrodes have raised safety concerns. This has prompted the development of novel aqueous multivalent cation storage systems, which can provide several benefits, including high capacity and energy density, rapid charge transfer, and low cost. With these advantages and the energy storage properties, multivalent cations such as Zn²⁺, Mg²⁺, Ca²⁺, and Al³⁺ have been applied to multivalent-ion hybrid capacitors (MIHCs), and the latest developments and design ideas for these have been recently reviewed. However, an overview from the perspective of materials with unique advantages and experimental designs remains limited. Carbon-based nanomaterials are leading candidates for next-generation energy storage devices due to their outstanding properties in MIHCs. The use of carbon-based nanomaterials is attractive because these materials are inexpensive, scalable, safe, and non-toxic. They are also bioactive at the anode interface, allowing them to promote electrochemical reactions with redox species that would otherwise not take place. This paper reviews recent advances in MIHCs and related carbon-based materials and discusses the utilization of carbon materials in MIHCs and ideas for material design, electrochemical behavior, energy storage mechanisms, electrode design, and future research prospects. Based on the integration of related challenges and development, we aim to provide insights and commercialization reference for laboratory research. For the first time, combined with global intellectual property analysis, this paper summarizes the current main research institutions and enterprises of various hybrid capacitors, and provides important technical competition information and development trends for researchers and practitioners in the field of energy storage. Simultaneously, we provide a perspective for the development of MIHCs, a description of the existing research, and guidelines for the design, production, commercialization, and advancement of unique high-performance electrochemical energy storage devices.