We have determined the c(2 × 2) structure formed on Cu(001) upon Li adsorption at 180 K by low-energy electron diffraction analysis. It is found that an overlayer of Li atoms sitting on the fourfold hollow sites (coverage 0.5) is preferred with a Cu-Li interlayer spacing of 1.96 ± 0.08 Å. The radius of the Li atom is 92% of the Li metallic one. The interlayer spacing between the first and second layers of Cu(001) is 1.81 ± 0.04 Å, and this is the same value of spacing of the clean Cu(001) surface.
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