The controlled incorporation of defect species in amorphous oxide (AO) for regulating charge transport properties is highly demanding and challenging, especially for resistive switching (RS) memories. Here, we use pulsed electron beam deposition technique to engineer the growth of AO films, which show a large decrease (â33\%) in the t2g-eg gap. Our collective experiments and density functional theory (DFT) based ab initio simulations reveal the presence of undercoordinated TiO5 units, causing a decrease in the t2g-eg gap. Further, the importance of TiO5 in facilitating excess electron localization is demonstrated, showing an evolution of a broad defect band within the energy gap. The origin of this band (singly charged oxygen vacancy) is resolutely established by X-ray photoelectron spectroscopy and electron paramagnetic resonance measurements and is also supported by calculated partial charge density and Bader charge analysis. The preeminence of singly charged oxygen vacancies cause a low-current level (up to 1-5 nA) RS operation with a gradual change of resistance states, which could set their path for the energy-efficient neuromorphic computing application. Finally, a new model based on probabilistic Markov chain algorithm is also developed to unfold the gradual change of resistance states from the fundamental defect interaction perspective. © 2019 American Chemical Society.