We report the determination of the complete LiHg shallow bound ground state potential curve by combination of laser-induced fluorescence spectroscopy of bound-bound transitions, photoassociation spectroscopy of bound-free transitions, and ab initio calculations. The results are evaluated by comparison of quantum mechanically simulated emission spectra with experimental data and used to describe spectroscopic features of the 2(2) Pi(3/2)-X(2) Sigma(1/2)(+) band as well as the photochemical formation via excitation of the lithium dimer.