A new electrode consisting of iron(III) hexacyanoferrate(II) known as Prussian blue and Dibenzo-18-crown-6 macrocycle ion-pair complex formed in presence of chloroform was studied for its electrochemical behavior in 0.1M KCl solutions. The ion-pair complex exhibited cyclic voltammetric response combining the Faradic redox characteristics of Prussian blue and the non-Faradic capacitance behavior of crown ether. Pseudo-capacitance values from the cyclic voltammetric measurements of the ion-pair complex showed a nine-fold increase as against the crown ether and a 1.5 times increase compared to Prussian blue. The ion-pair complex was chemically and electrochemically stable up to the cycled 1000 runs. Double potential step chronocoulometric measurements done at the lowest time scale of 10s showed specific capacitance value of 28.95×103 Fg−1 for the reduction step and 52.92×103 Fg−1 for the oxidation step. Such pseudo-capacitive values are the requisite of electrochemical capacitors that can provide huge power pulse within a very short time.