The room temperature ionic liquid (RTIL) 1-decyl-3-methyl-imidazolium bromide [C10mim][Br], dissolved in water, was studied using 1 H and 13 C NMR spectroscopy. The manifestation of phase transitions and fine features of molecular motion in NMR spectra upon changing temperature and composition have been analysed. The 1 H NMR line shape typical for anisotropic fluids with zero biaxiality (asymmetry) of magnetic shielding and the chemical shift anisotropy (CSA) of ca 0.33 ppm was observed and attributed to water molecules. CSA values for 13 C nuclei have been found in the range of 1.2-1.7 ppm. The difference between lyotropic liquid-crystalline (LC) ionogel phase and the solid one has been revealed, where the motions of RTIL and water molecules have been found to be dynamically segregated. The anisotropic 13 C NMR signal shape at 16.89 ppm shows the difference between LC ionogel and the lamellar phases, where usually the decreasing order parameter moving along hydrocarbon chain from the polar head is observed. It indicates, that the terminal −CH3 groups are more ordered and the supramolecular structures of [C10mim][Br], similar to some higher micellar RTIL aggregates are expected. In order to explain the experimental observations, the quantum chemistry DFT calculations of 1 H and 13 C magnetic shielding tensors of [C10mim] [Br] and various H-bond structures of H2O were performed.