A critical radiation damage assessment of the materials that will be present in a Geological Disposal Facility (GDF) for radioactive waste is a priority for building a safety case. Detailed analysis of the effects of high-energy α-particle damage in phyllosilicates such as mica is a necessity, as these are model structures for both the clay-based backfill material and the highly sorbent components of a crystalline host rock. The α-radiation stability of biotite mica [general formula: K(Mg,Fe)3(Al,Si3O10)(F,OH)2] has been investigated using the 5 MV tandem pelletron at the University of Manchester’s Dalton Cumbrian Facility (DCF) and both the microfocus spectroscopy (I18) and core X-ray absorption spectroscopy (B18) beamlines at Diamond Light Source (U.K.). Microfocus X-ray diffraction mapping has demonstrated extensive structural aberrations in the mica resulting from controlled exposure to the focused 4He2+ ion (α-particle) beam. Delivered doses were comparable to a-particle fluences expected in the highly active, near-field of a GDF. At doses up to 6.77 displacements per atom (dpa) in the region of highest particle fluence, biotite mica displays a heterogeneous structural response to irradiation on a micrometer scale, with sequential dilation and contraction of regions of the structure perpendicular to the sheets, as well as a general overall contraction of the phyllosilicate layer spacing. At the peak of ion fluence, the structure collapses under a high point defect density and amorphous areas are pervasive among altered domains of the original lattice. Such structural alterations are likely to affect the material’s capacity to sorb and retain escaped radionuclides over long timescales; increased edge site availability may favor increased sorption while interlayer uptake will likely be reduced due to collapse. Radiation-induced reduction of structural iron at the region of highest structural damage across an α-particle’s track has been demonstrated by Fe K-edge X-ray absorption near edge spectroscopy (XANES) and local structural disorder has been confirmed by analysis of both potassium K-edge XANES and Fe K-edge extended X-ray absorption fine structure analysis. An infrared absorption study of deformations in the OH− stretching region, along with electron probe microanalysis complements the synchrotron data presented here.