Zirconium and hafnium behave nearly identically in most geological processes due to their identical nominal ionic charge and similar radius. Some of the most pronounced exceptions from this rule are observed in fluoride-rich aqueous systems, suggesting that aqueous fluoride complexation may be involved in Zr/Hf fractionation. To understand the mechanisms causing this phenomenon, we investigated complexation of Zr4+ and Hf4+ in fluoride-rich (1.0 mol/kg HF) aqueous solutions at 40 MPa and 100–400 °C, using synchrotron X-ray absorption spectroscopy (X-ray absorption near edge structure and extended X-ray absorption fine structure) combined with classical and ab initio molecular dynamics simulations. The dominant experimentally observed complexes are [Zr(F,OH)4·2H2O]0 and [Hf(F,OH)4·2H2O]0, respectively. The first coordination shell comprises a distorted octahedron, with fluoride and hydroxide ligands at a similar mean radial distance (1.9–2.0 Å) from the central cation, and H2O ligands at a slightly greater distance (>2.1 Å). With increasing temperature, the H2O ligands move further out, causing first an increasing distortion of the octahedron and subsequently a partial transition to less hydrated complexes as a certain fraction of the H2O molecules move to the second shell at > 3 Å. As a consequence, the radial distance of the F- and OH– anions from the central cation, as well as the overall average radial distance of the first shell decreases due to decreased steric repulsion from the H2O ligands. Both experiments and simulations agree in that Hf forms slightly shorter bonds to its nearest neighbors than Zr. The results suggest two hypotheses for the mechanism of Zr/Hf fractionation during precipitation of minerals from fluoride-rich hydrothermal solutions: 1) The heavy twin (Hf) prefers the lower coordination (shorter bonds) and is thus less likely to enter into the higher coordination found in the solids. This mechanism would be analogous to equilibrium isotope fractionation. 2) The change of Hf into a higher coordination environment (e.g., from solution to solid) is slower because it forms stronger ligand-bonds than Zr. This would be analogous to reactive kinetic isotope fractionation. In either case mass dependent fractionation qualitatively matches the observations but mass independent effects on bond strength may also be significant. Quantitative investigations of these effects are needed and may also shed light on the currently still somewhat enigmatic fractionation behavior of Zr isotopes.