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Low temperature calorimetric measurements have been made on a series of binary aluminum alloys containing 1–10 at. % lithium. The heat capacity data are analyzed in terms of an electronic and a lattice contribution. Accordingly, the low level of lithium addition yields appreciable changes in the electronic density-of-states at Fermi level and the characteristic Debye temperature of lattice. These results reflect certain degrees of electron localization between aluminum and lithium atoms, providing a fundamental basis for solid solution strengthening in the lightweight materials with great potential in aerospace applications. © 2003 American Institute of Physics.