<jats:p> We report an experimental and theoretical study on the shift of the hyperfine splitting frequency of ground-state Li atoms in noble gases, He, Ne, Ar, and Xe. The frequency shift is due to the change in the electron-spin density at the Li nuclei induced by collisions to the noble-gas atoms. The electron density is calculated along the interatomic distance in a pseudopotential and a dispersion potential. Based on the measured and the calculated frequency shifts, we find the importance of attractive force in collisions to helium as well as heavy noble-gas atoms. Taking advantage of the simple energy structure of the Li atom, we obtain the s wave scattering length for free electrons on noble-gas atoms by using the hyperfine splitting frequency as a precise measure. </jats:p>