In recent years the sustainability crisis of especially lithium has become increasingly recognized by the public. The opposition to the continued use of lithium in future energy storage is most often justified by the expected resource depletion and concomitant future supply risk. Additional factors that should be considered include the inhomogeneous distribution of deposits, supply chain risks, the environmental impact of the necessary mining operations, and ethical concerns. To develop alternative energy storage solutions that are not based on critical resources, numerous research institutions and companies have dedicated a significant portion of their research and funding to commercially viable sodium-ion batteries (SIBs). The results of the research are currently starting to show, as large companies like CATL, Altris AB, and Natron Energy 9 prepare to produce their first SIBs. Despite the ongoing investigation of various cell chemistries involving potential cathode materials such as layered oxides, polyanionic compounds, and organic materials, the aforementioned companies share one unique attribute: they all focus on Prussian Blue-based compounds as the cathode material in their upcoming sodium ion battery production. Prussian Blue (PB, Na 0-2 Fe[Fe(CN) 6 ]) and its analogues (PBAs, Na 0-2 B[B ' (CN) 6 ] where B and B ' are transition metals) are strong contenders for a very sustainable, sodium based battery value chain. While the energy density of these materials is lower compared to lithium-ion batteries, their use will solve a lot of issues regarding the planned massive expansion of grid storage solutions. 9, On the atomic level, the lattice of Prussian Blue is made up of cyanide ligands, which interconnect high-spin, nitrogen coordinated iron atoms with low-spin carbon-coordinated iron atoms in an alternating fashion along all three spatial directions. During the (de)intercalation of charge carriers, such as sodium, both species of iron atoms are electrochemically active, with the C-coordinated iron being reduced first. Recently, the different stages of sodiation in Prussian Blue compounds are named after their characteristic color, meaning the fully desodiated, half sodiated and fully sodiated compounds are de-noted as Prussian Yellow, Prussian Blue and Prussian White, respectively. Still, the site occupancy statistics and resulting atomic structures during sodium (de)insertion and phase transition to the distorted phase of Na x Fe[Fe(CN) 6 ]) during battery charging remain elusive. This understanding is critical to making Prussian Blue a competitive commercial electrode material. The sodium orderings, which occur during reversible sodium (de)intercalation, may be influenced by the known charge ordering at the transition metal sites, although the exact mechanism remains unclear. The Na/vacancy orderings might determine the degrees of distortion as well as the stability of specific Na x Fe[Fe(CN) 6 ]) phases during sodium (de)intercalation, which is the primary focus of the current research.