More energy efficient desalination methods are needed to address global water scarcity. Capacitive deionization (CDI) is an emerging electrochemical desalination technology that could outperform other desalination technologies if new electrode materials were developed with high salt sorption capacity and efficiency. In this paper, we report on the desalination performance of thin-film sodium manganese oxide (NMO). We deposit thin-film MnO via atomic layer deposition (ALD), and electrochemically convert the MnO to NMO in NaCl (aq). Charge storage capacity is tuned with NMO thickness, and the relationship between charge storage capacity and reversible salt sorption is probed. NMO coated electrodes exhibit increases in charge storage capacity up to 170 times higher than uncoated electrodes. Electrochemical quartz crystal microbalance (EQCM) measurements reveal that thin-film NMO leads to the efficient electrochemical removal of Na+ ions. A hybrid CDI (HCDI) cell comprised of NMO-coated carbon nanotube (CNT) cathode and Ag nanoparticle-decorated CNT anode yields a∼ 20-fold improvement in charge storage over bare CNT electrodes. The HCDI cell has an anomalously high reversible charging efficiency, which we study using ab initio modeling and EQCM. This is the first CDI report using thin film NMO, and the high desalination efficiency we identify promises to facilitate the development of HCDI devices with enhanced performance.