MWCNT-based supercapacitors (SC) containing methylene blue (MB) as redox active electrolyte were studied. MWCNTs were employed as model of electrode active material due to their ideal double-layer behavior facilitates the investigation of the energy storage mechanisms involved. MB led to a cell capacitance enhancement equal to 4.5 times the original cell capacitance of MWCNTs in sulphuric acid with a capacitance reduction of only 12% after 6000 charge–discharge cycles. The potential evolution of each electrode during galvanostatic cycling revealed that MB redox reaction develops in both electrodes simultaneously in the voltage range of 0–0.104V and that this is the main cause of cell capacitance enhancement. Beyond this voltage range, the Faradaic contribution from the MB redox reaction decreases because the anode behaves as a capacitative electrode with a rather reduced charge-capacity due to the small surface area of MWCNTs. By means of a modified assembly composed of a Nafion membrane and MB and sulfuric acid solutions located in the cathode and anode compartments, respectively, it was demonstrated the limiting role of the capacitative electrode in the cell charge-capacity in this type of hybrid devices.