Local-order evolution around ions in aqueous solutions has been investigated between normal and hydrothermal conditions. The behavior of cations and anions in aqueous ZnBr2 solution were studied by performing x-ray absorption spectroscopy experiments at both Br and Zn edges. Extended x-ray absorption fine structure analyses are made on account of anharmonic treatment and multiple scattering contributions involving H atoms at the Br edge. The extended x-ray absorption fine structure results are coupled to x-ray absorption near-edge structure simulations in order to identify the complexes formed under normal and hydrothermal conditions. It appears that both Zn and Br ions are largely hydrated under normal conditions and that Zn-Br pairs are formed in hydrothermal conditions. This is related to an octahedral-to-tetrahedral evolution of the Zn local environment, the majority of Zn atoms being surrounded by water octahedra in normal conditions and by distorted tetrahedra involving Br and O atoms in hydrothermal conditions.