Bound and free water within dough strongly affect its rheological behavior and processability, as well as its gluten network. Depending on its total content and on the characteristics of flour constituents, water can be both bound to components and free in the dough. The equilibrium between bound and free water directly impacts the elasticity and extensibility of dough and therefore controls the texture of final products. In this study, Nuclear Magnetic Resonance (NMR) was used to assess the relaxation behavior with the focus on water. The proton spin-spin relaxation measurements were carried out at 20 MHz with a Bruker Minispec mq20 NMR spectrometer (Bruker, Rheinstetten, Germany). The transverse relaxation time in a spin locking field (T1?) was determined at 25°C following the Carr–Purcell–Meiboom–Gill (CPMG) sequence. The data were analyzed by the continuous distribution model. The dough was prepared with commercial semolina, which was mixed with water in a Brabender Mixer 350 (Brabender® GmbH, Duisburg, Germany) to reach three different levels of water content (30, 50, and 70%, based on semolina weight) and to study the water distribution as a function of the water total content. The dough characterization was carried out also comparing the T1? distribution of semolina dough with that of starch-water and gluten-water mixtures and also of pure starch and gluten to assess the role of each flour component. Additionally, the semolina dough sample was compared with a sample prepared with pastry flour, with a lower content of proteins, to investigate the different behavior as a function of the gluten amount. It was found that the dough presents three relaxation processes: one, very fast, is related to crystalline starch, while the other two are characteristic of two water populations, water in intragranular and in extragranular regions of starch, respectively. The comparison with pastry flour showed that the dough prepared with the latter one was less homogenous than the semolina one, with a clear distinction between free and bound water, while the semolina dough seemed to contain several water populations differently bounded, that were responsible for a broader peak at medium water content (around 50%).