Metal recovery coupled with CO2 mineralization from sustainable sources, such as seawater, has garnered significant attention from environmental science and resource utilization perspectives. Herein, an earth‐abundant and efficient Fe/Fe3C@Fe‐N‐codoped carbon@carbon nanotube (Fe/Fe3C@Fe‐NC@CNT) hybrid cathodic catalyst is introduced for electrochemically extracting magnesium and calcium from desalination brine while capturing CO2 to produce valuable Mg(OH)2 and CaCO3. The Fe/Fe3C@Fe‐NC@CNT, featuring the combination of single‐atomic Fe sites and graphitic layer‐wrapped Fe/Fe3C nanoparticles encapsulated within N‐doped mesoporous carbon tubes, achieves over 90% of Ca2+ and Mg2+ metal cations recovery efficiency at 25 mA cm−2 for 6 h. More importantly, the Fe/Fe3C@Fe‐NC@CNT hybrid catalyst efficiently suppresses the competitive hydrogen evolution side reaction even at high currents and boasts a wider operating potential range compared to benchmark Pt/C, enhancing the metal recovery efficiency and CO2 capture capability. These findings underscore the potential of the Fe/Fe3C@Fe‐NC@CNT hybrid catalyst in revolutionizing brine management and waste stream handling, offering a promising and sustainable solution to these critical environmental challenges.