Several promising applications of amorphous titanium dioxide, aTiO2, have appeared recently, but thecorrelation between electronic properties and atomic short-range structural order is poorly understood. Herein weshow that structural disorder yields local undercoordinated TiOx units which influence electronic hybridization ofTi-[4p] andTi-[3d] orbitals with a lowcrystal-field splitting [E(eg)-E(t2g) = 2.4 ± 0.3 eV]. The short-range orderand electronic properties of aTiO2 thin-film oxides are described through an integrated approach based on x-rayabsorptionexperiments and ab initio computational simulations where the energy splitting of the electronic levelsin the Ti-[4p-3d]manifold are analyzed. Structural disorder provides enough p-d orbitalmixing for the hybridizedelectronic transitions from the Ti-[1s] core level into the [Ti-t2g] and [Ti-eg] bands [1s → 4p-3d excitations],to be allowed. This yields an intense pre-edge structure in the Ti K-edge x-ray-absorption near-edge structurespectrum of aTiO2, which is consistent with the projected density of states on the photoabsorbing Ti atoms.