The structure of aqueous magnesium nitrate solution is gaining significant interest among researchers, especially whether contact ion pairs exist in concentrated solutions. Here, combining X-ray diffraction experiments, quantum chemical calculations and ab initio molecular dynamics simulations, we report that the [Mg(NO₃)₂] molecular structure in solution from the coexistence of a free [Mg(H₂O)₆]²⁺ octahedral supramolecular structure with a free [NO₃(H₂O)_n]⁻ (n = 11–13) supramolecular structure to an [Mg²⁺(H₂O)_n(NO₃⁻)_m] (n = 3, 4, 5; m = 3, 2, 1) associated structure with increasing concentration. Interestingly, two hydration modes of NO₃⁻—the nearest neighbor hydration with a hydration distance less than 3.9 Å and the next nearest neighbor hydration with hydration distance ranging from 3.9 to 4.3 Å—were distinguished. With an increase in the solution concentration, the hydrated NO₃⁻ ions lost outer layer water molecules, and the hexagonal octahedral hydration structure of [Mg(H₂O)₆²⁺] was destroyed, resulting in direct contact between Mg²⁺ and NO₃⁻ ions in a monodentate way. As the concentration of the solution further increased, NO₃⁻ ions replaced water molecules in the hydration layer of Mg²⁺ to form three-ion clusters and even more complex chains or linear ion clusters.