In this work, we utilise a combination of theory, computation and experiments to understand the early events related to the nucleation of Ag filaments on α-Ag₂WO₄ crystals, which is driven by an accelerated electron beam from an electron microscope under high vacuum. The growth process and the chemical composition and elemental distribution in these filaments were analysed in depth at the nanoscale level using TEM, HAADF, EDS and XPS; the structural and electronic aspects were systematically studied in using first-principles electronic structure theory within QTAIM framework. The Ag nucleation and formation on α-Ag₂WO₄ is a result of the order/disorder effects generated in the crystal by the electron-beam irradiation. Both experimental and theoretical results show that this behavior is associated with structural and electronic changes of the [AgO₂] and [AgO₄] clusters and, to a minor extent, to the [WO₆] cluster; these clusters collectively represent the constituent building blocks of α-Ag₂WO₄.