Directional Compton profiles ͑CP's͒ of Li metal were measured for 11 directions of the momentum transfer q with 0.14 a.u. ͑a.u.ϭatomic units: បϭeϭmϭ1͒ momentum-space resolution using synchrotron radiation from the DORIS ͑Doppel-Ring-Speicheranlage͒ storage ring monochromatized to 31 keV. Both the total valence-electron CP's and the directional differences of the CP's exhibit considerable deviations from the most recent density-functional calculations, performed by Sakurai et al. ͓Phys. Rev. Lett. 74, 2252 ͑1995͔͒ within the limits of the local density approximation. These discrepancies are attributed to self-energy effects connected with the excitation of so-called plasmaron modes. The three-dimensional ͑3D͒ valence-electron momentum density, ͑p͒, as well as the 3D occupation number density N͑k͒, were reconstructed using the Fourier-Bessel method. The reconstructed ͑p͒ exhibits clear evidence of higher momentum components due to 110 umklapp processes. The reconstructed N͑k͒ enables a direct experimental access to the Fermi-surface anisotropy of Li, which was found to be 3.6Ϯ1.1%. The reconstructed N͑k͒ for kʈ ͓001͔ was fitted to a model with the renormalization factor z as the only free parameter, which was found to be zϭ0.1Ϯ0.1.