Prussian white (PW), Na2Fe[Fe(CN)6]·zH2O, is an attractive positive electrode material in Na-ion batteries. The structure of PW changes depending on the sodium and water content, affecting the material's performance. For example, the presence of water stabilizes the structure for ion transport, however, water can cause unwanted side reactions with the electrolyte. In contrast, dehydration results in structural collapse and large volume changes during ion extraction and insertion, which could lead to capacity fade over time. Details about the different structures are necessary to improve the material for Na-ion batteries. We recently showed that two room-temperature structures exist for PW (P2_1/n and R-3 at 35 °C), where the water becomes disordered during this phase transition. Upon dehydration, the symmetry is maintained, but the magnitude of the distortions increases significantly, resulting in structural collapse and peak broadening. Therefore, neutron total scattering is needed to look into the local structure of these materials. For both the hydrated and dehydrated materials, the local structure (1-5 Å) differs greatly from the average structure involving large distortions away from the average octahedra. To model this, big-box modeling is needed since conventional small-box modeling (real-space Rietveld refinements) fails to model both the very local and the average structure. The goal is to determine the position of water in the two room-temperature structures, the local coordination of sodium, and the distortions and rotations of the iron octahedra in both the hydrated and dehydrated materials using Reverse Monte Carlo simulations (RMCProfile). Understanding the local structure of PW will aid the development of new improved energy materials comprised of PW.