Amorphous transition metal oxides (aTMOs) are used as multifunctional materials in many technological applications. A detailed understanding of the electronic density of states is a necessary prerequisite for modeling their functional properties. The electronic properties, however, are structure-dependent making the description of the electronic structure of disordered and amorphous materials challenging. Here we present a scheme based on obtaining atomic model structures from simulations of experimental X-ray-Absorption spectra, together with first principles electronic structure calculations. This approach provides a self-consistent framework to assess fundamental electronic processes in aTMOs and can be applied to the study of disordered and amorphous materials in general.