The results of ab initio calculations of the adiabatic potential energy surfaces for the proton-bound [FHF]- system at different F-F distances have been rationalized in the framework of the vibronic theory. It is shown that the instability of the symmetric D∞h structure at increased F∙∙∙F distances and the proton displacement to one of the fluorine atoms are due to the pseudo Jahn–Teller mixing of the ground electronic state 11Σg with the lowest excited state of 1Σu symmetry through the asymmetric σu vibrational mode.