To support the vitrification of high-Fe radioactive wastes stored at the Hanford Site, USA, this study has considered the structural impacts of iron oxide on the borosilicate glass network. Three series of borosilicate glass were designed and prepared, from simple sodium borosilicate glasses (SCFe series), to more complex borosilicate glasses (CCFe Series), to full Hanford analogue glasses (HAFe series). These three glass series were analysed using XRF and ICP-OES, with XRD to study any crystalline phases. The SCFe and CCFe samples were X-ray amorphous, while the two highest-iron HAFe samples showed an iron-rich spinel phase present in the glass. 57Fe Mössbauer and Fe K-edge XANES spectroscopies showed that the iron exists exclusively as Fe3+ in predominantly distorted tetrahedral structures ([4]Fe3+), with evidence for lower abundances of higher-coordinated [5 or 6]Fe3+. Raman, B K-edge, and B 1s, Si 2p XPS spectroscopies qualitatively demonstrated that Fe3+ preferentially integrates into the borosilicate network through the silicate sub-network in the simplest glasses, the SCFe series, whereas in more complex borosilicate glasses it preferentially integrates through the borate sub-network. The [4]B3+ fraction for the SCFe and CCFe glasses was shown to be ~0.45 and ~0.35 respectively, with minimal changes as a function of Fe content. This suggests that while the Fe ions may bond into the borate sub-network, the concentration of Fe ions has no effect on the boron coordination and is therefore unlikely to be competing with the [4]B3+ groups for charge compensation, qualitatively supporting the presence of complex competition between multiple FeO4– / BO4– / AlO4– tetrahedral avoidance hierarchies.