This manuscript reports on the novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH4SCN). The effect of salt concentration, electrode porosity and current collectors on the capacitance value, system stability, and power performance has been investigated. Therefore, thiocyanate-based electrolytes were recognized as cheap and highly conductive electrolytic solutions (up to 401 mS cm-1 for NH4SCN at RT) allowing a cell voltage of 1.6 V in a symmetric carbon/carbon system to be achieved. At the same time, they display an attractive redox activity, enhancing the energy of the device with a good performance during cycling.