Three different phases of thorium(IV) oxalate hydrate [Th(C₂O₄)₂·xH₂O] with different water contents, namely, the hexahydrate, dihydrate, and anhydrous phases, were prepared by thermal treatment of the as-precipitated hydrated thorium(IV) oxalates. With the change in water content, the structure changes from monoclinic (C2/m) for the hexahydrate to monoclinic (C2/c) for the dihydrate and finally to a highly disordered phase for the anhydrous state. The local coordination around the Th⁴⁺ ions in these structures was monitored by using Eu³⁺ ions as luminescent probes. The analyses of the emission spectra owing to the electric-dipole transitions (EDTs) and magnetic-dipole transitions (MDTs) of the Eu³⁺ ions in the different phases revealed that the site symmetry around the Th⁴⁺ ions decreases systematically from symmetric to highly distorted with the decrease in water content. The relative intensity ratios (I) of the EDT to MDT for x= 6, 2, and 0 are 2.36, 3.32, and 4.23, respectively. The analyses of the delay curves corresponding to the ⁵D₀ level of the Eu³⁺ ions indicated biexponential decay with varying lifetimes, which suggests two possible environments around the Eu³⁺ ions and a possible role of oxygen vacancies. The long-lived species is expected to be distant from the charge-compensation defects, whereas the short-lived species is nearer to the charge-compensation defect. Tunability of the emission with the excitation wavelength is observed for all phases and is attributed to the presence of defect-mediated broad emission in the blue region and red-orange emission from the Eu³⁺ ions.