The O-17 and H-1 hyperfine interactions of water ligands in the Ti(III) aquo complex in a frozen solution were determined using Hyperfine Sublevel Correlation (HYSCORE) and Pulse Electron Nuclear Double Resonance (ENDOR) spectroscopies at 9,5 GHz The isotropic hyperfine interaction (hfi) constant of the water ligand O-17 was found to be about 7.5 MHz. H-1 Single Matched Resonance Transfer (SMART) HYSCORE spectra allowed resolution of the hfi interactions of the two inequivalent water ligand protons and the relative orientations of their hfi tensors. The magnetic and geometrical parameters extracted from the experiments were compared with the results of DFT computations for different geometrical arrangements of the water ligands around the cation. The theoretical observable properties (g tensor H-1 and O-17 hfi tensors and their orientations) of the [Ti(H2O)(6)](3+) omplex are in quantitative agreement with the experiments for two slightly different geometrical arrangements associated with D-3d and C-i symmetries.