Elemental analysis and TGA (Figure and Table ) result in structural formulae of K 0.55 Fe[Fe(CN) 6 ] 0.92 •3.3H 2 O and K 1.04 Fe[Fe(CN) 6 ] 0.94 •4.1H 2 O for HC-PB and LC-PB, respectively. Given that values of <1 were observed for [Fe(CN) 6 ] 4-, defect sites are concluded to be present in both samples. Fe K-edge EXAFS analysis of the samples is indicative of the PB structure (Figures and), with features associated with the Fe-C/N 1 st and 2 nd shells and the Fe-Fe 1 st shell. The intensity of Fourier Transform magnitude features is similar between samples, indicating that the short-range order was comparable. Room temperature 57 Fe Mossbauer spectra of the two samples (Figure and Tables &) also show limited differences, with similar average quadrupole splittings and the ratio of Area Fe(III) : Area Fe(II) is equal to 1. The high spin Fe 3+ component of the spectra required fitting with two doublets that are associated with the ideal Fe(NC) 6 site and another with partial water coordination, demonstrating comparable defects exist in both samples. The results are in contrast to the impactful assumption that small crystallite size equated to a more defective structure, which was applied in previous studies of PB electrochemical stability. In the present study, both high and low crystallinity samples contain a notable, but comparable, number of defects, despite their very different crystallite size.