Electron distribution in liquid metals and charge transfer in liquid alloys are qualitatively and quantitatively discussed in terms of the structure factors and the thermodynamic quantities obtained experimentally. The electron distribution around an ion in liquid metals has been derived from the difference in structure factors determined by X-ray and neutron-diffraction methods with the help of a theoretical calculation of the electron–electron correlation function. Charge transfer in liquid alloys is also estimated by using the partial structure factors in the long-wavelength limit and the Thomas–Fermi screening theory. The charge-transfer effect in liquid alloys is also verified by the measurements of partial structure factors and magnetic susceptibilities.