This work presents a method for modelling the local structure of an amorphous material at the quantum mechanical level of accuracy, that is one which describes the electronic structure of an amorphous solid using first principles methods, which is then applied to a-Al2O3. This method utilizes both first principles calculations and high-quality spectroscopy to confirm the detailed electronic structure of a-Al2O3. The novelty of our approach lies in the integration of locally sensitive experimental techniques with spectroscopy calculated from first principles We obtain NMR spectra at fields up to 1 GHz, which is the current state-of-the-art in solid state NMR and show that our DFT-based model contains the same structural features captured by these experimental measurements. The atomic level accuracy of this model enables us to identify two distinct five-fold coordination geometries present in a-Al2O3, and the orbital character of electronic states at the Al pre-edge of the absorption spectrum, which are unique to a-Al2O3. We calculate an average electronic density of states on our model, in a computationally efficient and accurate manner, thereby opening the door for further investigation into amorphous electronic structure.