Ab initio perturbed ion calculations were performed for the cubic, orthorhombic, hexagonal, and monoclinic phases of PbF 2 . A complete characterization of these phases was achieved in terms of the potential energy surfaces, the equations of state, and the phase-transition pressures. Thermal effects were included via a quasi-harmonic nonempirical Debye model. The internal parameters of the unit cell of each phase were reoptimized at each volume to generate the energy surface. The calculated results are in good agreement with the experi-mental data available for the cubic and orthorhombic phases. The results predict the hexagonal phase to be the high-pressure post-cotunnite structure for PbF 2 , since the monoclinic phase is seen to collapse into the hex-agonal phase during the optimization at high pressures.