The ion pairing structure of Ni(Br)(2) solutions (0.2 and 0.4 molal) under supercritical conditions was determined using x-ray absorption fine structure (X4FS) spectroscopy. These first measurements of the average bulk structure show that approximately one Br-counterion is associated with each Ni2+. The Ni2+-to-Br- distance of 2.40 Angstrom is very accurately determined and the strength of this interaction, as indicated by the Debye-Waller factor (sigma(2) = 0.009 Angstrom(2)), shows that the bromine anion is very tightly bound to the nickel cation under these supercritical conditions. In addition to the onset of ion pairing interactions, there is also a dramatic transition in the hydration structure. Results show a loss of about 50% of the waters in the first shell upon going from ambient to a hydrothermal condition of 425 degrees C and 690 bar. Finally, we use molecular dynamics simulations with refined intermolecular potentials to directly calculate XAFS spectra that are shown to quantitatively reproduce the experimental results for the ion pair and hydration structure.