The aim of this work was to prepare a new hydrogel based on nanohydroxyapatite (nFAP, 10% w/w) and fluorides (4% w/w), both of which are used as sources of fluoride ions in the treatment of dentin hypersensitivity, and to characterize its physicochemical properties. The release of fluoride ions from 3 gels (G-F, G-F-nFAP, and G-nFAP gel) was controlled in Fusayama–Meyer artificial saliva at pH 4.5, 6.6, and 8.0. The properties of the formulations were determined by an analysis of viscosity, a shear rate test, a swelling study, and gel aging. Various methods, i.e., FT-IR spectroscopy, UV-VIS spectroscopy, and thermogravimetric, electrochemical, and rheological analysis, were used for the experiment. The profiles of fluoride release indicate that the amount of fluoride ions released increases with a decrease in the pH value. The low pH value facilitated water absorption by the hydrogel, which was also confirmed by the swelling test, and it promoted the exchange of ions with the surrounding environment. Under conditions similar to physiological conditions (at pH 6.6), the amounts of fluorides released into artificial saliva were approximately 250 µg/cm2 and 300 µg/cm2 for the G-F-nFAP hydrogel and G-F hydrogel, respectively. The aging study and properties of the gels showed a loosening of the gel network structure. The Casson rheological model was used to assess the rheological properties of the non-Newtonian fluids. Hydrogels consisting of nanohydroxyapatite and sodium fluoride are promising biomaterials in the prevention and management of the dentin hypersensitivity.