In this paper we have focused on fundamental processes that are important for understanding the electrical properties of materials, both single crystal minerals and igneous rocks, both laboratory-grown and from natural environments. The prevailing view in the geophysics community is that the electrical conductivity structure of the Earth’s continental crust over the 5-35 km depth range can best be understood by assuming the presence of intergranular fluids and/or intergranular carbon films. Based on studies of melt-grown MgO, magma-derived sanidine and anorthosite feldspar and upper mantle olivine single crystal we present evidence for the presence of electronic charge carriers, the importance of which has been largely ignored. These charge carriers derive from peroxy defects, which are introduced during cooling, under non-equilibrium conditions, through a redox conversion of pairs of solute OH– arising from the solid state dissolution of H2O. It can be shown that, during reheating, the peroxy defects become thermally activated in a 2-step process. Step 2 leads to the release of defect electrons in the oxygen anion sublattice. Known as positive holes and symbolized by h•, these electronic charge carriers are associated with energy states at the upper edge of the valence band. They are highly mobile. Chemically equivalent to O– in a matrix of O2– they are highly oxidizing. However, though metastable, the h• can exist in minerals, which crystallized in highly reduced environments. The h• appear to control the electrical conductivity of crustal rocks over much of the 5-35 km depth range. We make the extraordinary and seemingly paradoxial claim that MgO crystals, grown from the melt under the viciously reducing conditions of a carbon arc fusion furnace, contain peroxy defects in their crystal structure, hence oxygen in the valence state 1–. When the peroxy defects break up, they release positive hole charge carriers, formally defect electron in the oxygen anion sublattice, equivalent to O– in a matrix of O2–. These positive holes have two outstanding properties: they are highly mobile and highly oxidizing.