Hybrid nanocomposite materials Bu4NBF4–MgO were obtained using a nanocrystalline MgO with a specific surface area of 324 m2/g and the grains size of 5.1 nm. As a result of the strong adhesion, the salt transforms into an interface-stabilized amorphous state within the thin layer near the interface. The analysis of the DSC data allowed one to estimate the concentration and the thickness of this amorphous layer as 4.8 nm. The amorphous interface phase has an enhanced ionic conductivity. As a result, conductivity of the nanocomposite increases with the concentration of the amorphous phase and reaches 1.1 × 10−3S/cm at 150 °C at a concentration of the MgO additive x = 0.90 corresponding to the maximum content of the amorphous phase. The conductivity of the nanocomposite is by three orders of magnitude higher than the conductivity of pure Bu4NBF4. The nanocomposites are electrochemically stable up to 2.5 V. At high concentrations of MgO when the total volume of the salt is small the composites become nano- and mesoporous.