We report electrical conductivity measurements on metal‐olivine systems at about 5 and 6 GPa and up to 1,675°C in order to investigate the electrical properties of core‐mantle boundary (CMB) systems. Electrical experiments were conducted in the multianvil apparatus using the impedance spectroscopy technique. The samples are composed of one metal layer (Fe, FeS, FeSi2, or Fe‐Ni‐S‐Si) and one polycrystalline olivine layer, with the metal:olivine ratio ranging from 1:0.7 to 1:9.2. For all samples, we observe that the bulk electrical conductivity increases with temperature from 10−2.5 to 101.8 S/m, which is higher than the conductivity of polycrystalline olivine but lower than the conductivity of the pure metal phase at similar conditions. In some experiments, a conductivity jump is observed at the temperature corresponding to the melting temperature of the metallic phase. Both the metal:olivine ratio and the metal phase geometry control the electrical conductivity of the two‐layer samples. By combining electrical results, textural analyses of the samples, and previous studies of the structure and composition of Mercury's interior, we propose an electrical profile of the deep interior of the planet that accounts for a layered CMB‐outer core structure. The electrical model agrees with existing conductivity estimates of Mercury's lower mantle and CMB using magnetic observations and thermodynamic calculations, and thus, supports the hypothesis of a layered CMB‐outermost core structure in the present‐day interior of Mercury. We propose that the layered CMB‐outer core structure is possibly electrically insulating, which may influence the planet's structure and cooling history.