The local structure of fluorine incorporated in crystalline germanium by ion implantation and annealing has been investigated by x-ray absorption near edge structure (XANES) spectroscopy. The XANES spectra of different FmVn complexes have been simulated by ab initio calculations and compared with the experimental spectrum. In our study, we show that most of the F in Ge forms F6V2 complexes, lengthening the Ge–Ge distances in the close proximity.