For the effective reduction of global CO2 emissions, it is essential to develop and deploy efficient and cost-effective technologies for CO2 capture, especially from large point sources. We recently developed an electrochemically mediated amine regeneration (EMAR) system to replace traditional thermal desorption for the capture of CO2 from post-combustion flue gases. Despite EMAR effectiveness on a laboratory scale, concerns regarding the high gas-to-liquid ratio in the electrochemical cell and long-term instability of the electrodes need to be addressed before further scale-up of the process to a pilot plant and beyond can be entertained. Accordingly, we investigated the effect of using sodium dodecyl sulfate (SDS) as an anionic surfactant and dodecyltrimethylammonium bromide (DTAB) as a cationic surfactant on the process operation. It was found that it is advantageous to use an anionic surfactant for a system such as EMAR that contains hydrophilic electrodes and a positively charged electrochemically active species. The overall cell resistance was notably reduced when SDS anionic surfactant was used. The precipitation of copper particles observed in the anode outlet when no surfactant was used was effectively avoided when SDS was added to the electrolyte, resulting in electrode stability. In addition, smaller gas bubbles were produced in the presence of the SDS surfactant, which resulted in less blockage of the electrode by the gas with a resultant lower cell potential under constant current conditions, driving more efficient CO2 desorption. This led to an approximate 25% reduction in the electrochemical energy requirement, the lowest ever achieved experimentally for the EMAR process. Overall, the addition of a very low concentration of SDS resulted in the successful circumvention of the important problems faced by the EMAR system regarding further scale-up.