Nowadays, supercapacitors are at the forefront of technologies for energy storage systems. The storage capability of supercapacitors is primarily influenced by the electrode material and its mechanism of charge storage that dictates the charge transfer or accumulation processes at the electrode–electrolyte interface. By employing various engineering and functionalization strategies, the charge storage performance, response rate and operational lifetime can be optimized. For instance, by increasing the specific surface area of the active material with the preparation of metal foams, the mass loading is optimized, which represents an interesting strategy to design advanced electrode architectures for supercapacitor devices with enhanced metrics. These strategies aim to enhance the physical–chemical properties of the materials, including the availability of active charge storage sites, conductivity and redox activity. In the following chapter, we will describe and analyse the electrochemical behaviour of metal foam-based electrodes for supercapacitors and their most important features.