A novel strategy for the development of high energy density supercapacitors (SC) is explored. The new devices contain two electrolytes that are different in nature, an aqueous electrolyte in one half-cell and an ionic liquid in the other. These systems, referred to as biliquid SCs, make it possible to combine the best electrode/electrolyte in terms of individual electrode capacitance and cathodic/anodic stability limits. Furthermore, other asymmetries that combine different electrodes, electrolytes and storage mechanisms can be incorporated. Synchronous cyclic chronopotenciometry was used to monitor the performance of these novel complex systems. It is expected that this approach will help scientists working in this field to develop new devices that overcome the energy density limitations of current SCs, thereby extending the scope of their application.