A lithium silicon alloy was synthesized by mechanical alloying method. Hydrogen storage properties of this Li–Si–H system were studied. During hydrogenation of the lithium silicon alloy, lithium atom was extracted from the alloy and lithium hydride was generated. Equilibrium hydrogen pressures for desorption and absorption reactions were measured in a temperature range from 400 to 500°C to investigate the thermodynamic characteristics of the system, which can reversibly store 5.4mass% hydrogen with smaller reaction enthalpy than simple metal Li. Li absorbing alloys, which have been widely studied as a negative electrode material for Li ion rechargeable batteries, can be used as hydrogen storage materials with high hydrogen capacity.