Abstract : Experiments were conducted to determine the electrical properties of silicate glasses and liquids from Mt Vesuvius and Kilauea volcanoes using impedance spectroscopy. A methodological study of the two and four electrode measurements improved the quality of the electrical measurements. Measurements were performed between 400 and 1400°C, from 0.1 to 400MPa and for oxygen fugacities ranging from 10-8 to 0.2 bar. The electrical conductivity increases with increasing temperature, water content, sodium content and with decreasing pressure and fO2. Arrhenius laws were determined for glasses and liquids to investigate the transport properties. Activation energies from 60 to 150kJ/mol and an activation volume of 20cm3/mol were calculated. A semi-empirical method was deduced to estimate the conductivity of a wide range of melts. A geophysical application of our results consisted in the forward modelling of the conductivity of Mt Vesuvius. Transfer functions are explained by the only presence of a brine. Its high conductivity makes difficult the detection of a deeper magmatic body. Still, our simulations demonstrated that present geophysical data are compatible with a crystallized magma reservoir or a hotter magma interconnected in the surrounding carbonates. A geochemical application consisted in the monitoring in real-time of redox kinetics in basaltic liquids, using the time-dependence of electrical conductivity following fO2 step changes. The evolution of the conductivity with time, related to sodium mobility, is identical to that of the ferric/ferrous ratio of the melt. Reduction under CO-CO2 and oxidation in air are diffusion-limited, while oxidations under CO2 are not, probably due to gas/melt interface reactions. High calculated diffusivities and activation energies have been explained by redox mechanisms involving cooperative alkali, divalent cation and oxygen fluxes.