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Abstract Electro-scrubbing is being developed as a futuristic technology for the removal of air-pollutants. To date, only one homogeneous mediator for the removal of air pollutants has been generated in each experiment using a divided electrolytic flow cell in an acidic medium. This paper reports the concurrent generation of two homogenous mediators, one at the anodic half-cell containing an acidic solution and the other at the cathodic half-cell containing a basic solution. The concept was inspired by the change in pH that occurs during water electrolysis in a divided cell. A 10 M KOH electrolyte medium assisted in the electrochemical generation of low valent 14% Co1+ ([CoI(CN)5]4−) mediator formed from reduction of [CoII(CN)5]3− which was accompanied by a change in the solution 'oxidation reduction potential' (ORP) of −1.05 V Simultaneously, 41% of Co3+ was generated from oxidation of CoIISO4 in the anodic half-cell. No change in the solution ORP was observed at the cathodic half-cell when both half-cells contain 5 M H2SO4, and Co3+ was formed in the anodic half-cell. An electro-scrubbing approach based on the above principles was developed and tested on gaseous-pollutants, CH3CHO and CCl4, by Co3+ and Co1+, respectively, with 90 and 96% removal achieved, respectively.