•Uses wastewater to capture CO2 from ambient air and convert it to useful products.•Energy can be generated during microbial electrolysis and carbon capture.•Carries significant environmental and economic potential in large scale. This study reports that wastewater can be used to capture and store CO2 directly from ambient air and produce energy. The proof-of-concept system consisted of an ion exchange resin column that captures and concentrates ambient CO2 using a moisture-driven cycle. The concentrated CO2 was then transferred into a microbial electrochemical carbon capture (MECC) reactor for carbon sequestration and hydrogen production. Data from an average batch cycle showed that approximately 8mmol/L CO2 was captured in the MECC cathode when 0.14g/LCOD was removed in the anode. With 90% hydrogen conversion efficiency, the energy intensity and CO2 absorption from the process could be 11.3kJ/gCOD and 0.49gCO2/gCOD respectively. If the proposed process is applied, over 68milliontons of atmospheric CO2 can be captured yearly during wastewater treatment in the US, which equates to significant economic values if CO2 taxes were to be implemented more widely.