Here we present the electrochemistry based on the formation/dissolution reactions of two dual-RICs(Redox ionic complexes) : HV²⁺ and Br^-. During a charge process, HV²⁺ is reduced to form a solid [HV^+··Br^-] on an anode, while Br^- is oxidized to from a solid [HV²⁺·2Br₃^-] on a cathode, resulting in significant suppression of self-discharge in the Redox-EC(electrochemical capacitors). We found that [HV^+··Br^-]_(s) formed on Pt UME is electrochemically further reduced through proton coupled electron transfers (PCETs). Also, we deciphered stochastic current spikes associated with the galvanic exchange reaction between a [HV^+··Br^-]_(s) film and a [HV²⁺·2Br₃^-] particle in an acidic and neutral solution, and proposed the different electro-reduction mechanism of [HV²⁺·2Br₃^-] particles on a modified Pt UME with [HV^+··Br^-] in acidic condition from that in a solution with neutral pH.