as Li and Ni will be intensively used in large batteries for electric vehicles (EVs). These elements may be fully consumed for EV applications, so it will be impossible to have enough of them for batteries designed for large energy storage. These concerns have produced increasing interest in alternative technologies, with sodium-based storage chemistry among the leading modalities. [2] Reversible sodium intercalation received attention as one of the leading post-lithium battery technologies, as it combines several very attractive properties. Various merits are attributed to Nabased cells, in particular safety, low cost, Earth abundance, and environmental friendliness. [2c,3] As a consequence, many cathode compounds that can be utilized in sodium batteries were recently reported, including organic compounds, [4] polyanionic compounds, [5] and transition metal oxides. [6] Among them, manganese-based cathode materials have attracted much attention due to their low cost and significant Earth abundance.The tunnel-type sodium manganese oxide Na 0.44 MnO 2 is particularly attractive owing to its unique large tunnels suitable for sodium intercalation. [7] The crystal structure of Na 0.44 MnO 2 is shown in Figure 1a. There are five distinct crystallographic manganese sites and three sodium sites, where Mn(1) and Mn(2) are occupied by Mn 3+ , and Mn(3), Mn(4), and Mn (5) are occupied Mn 4+ . [8] The structural frame is built up of double and triple linear chains with edge-shared MnO 6 octahedra and single chains of edge-shared MnO 5 square-pyramids. Each chain is aligned parallel to the c-axis and connected to neighboring chains via a corner-sharing of the polyhedra, resulting in two types of tunnels: the 1D tunnels occupied by Na(1) atoms ( Figure 1b) and the 2D tunnels occupied by Na(2) and Na(3) atoms, which are positioned in large zig-zag shaped cavities (Figure 1c). Interestingly, unlike common layered oxides, such a structure is very stable in aqueous solutions, even upon electrochemical sodium intercalation/deintercalation. [7f,9] Thus, recently many publications focused on Na 0.44 MnO 2 as a particularly promising cathode material for both aqueous and nonaqueous sodium-ion batteries. [10] However, to our knowledge, their sodium storage mechanisms were not determined experimentally due to the complex multifold oxidation/reduction steps, while ab initio calculations were reported. [8] Besides that, Tunnel-type sodium manganese oxide is a promising cathode material for aqueous/nonaqueous sodium-ion batteries, however its storage mechanism is not fully understood, in part due to the complicated sodium intercalation process. In addition, low cyclability due to manganese dissolution has limited its practical application in rechargeable batteries. Here, the intricate sodium intercalation mechanism of Na 0.44 MnO 2 is revealed by combination of electrochemical characterization, structure determination from powder X-ray diffraction data, 3D bond valence difference maps, and barrier-energy calculations of the sodium ...