This study aims to develop a nano-sized fluoridated layered double hydroxide (LDH)-based release system via hydrothermal treatment for the controlled delivery of fluoride (F-) ions in the oral environment. The synthesis of conventional LDH-type (C-LDH) precursor nanomaterials was conducted using a co-precipitation method at constant pH, and the nanoparticulate-LDH (N-LDH) was synthesized by a hydrothermal procedure. Fluoride LDH (F-LDH) products were obtained through indirect synthesis using the precursor ion-exchange technique by varying the agitation time (2 and 24 h) and temperature (25 and 40 °C) to produce 12 material samples. The materials were characterized by energy dispersive x-ray, hexamethyldisilazane, digital radiography x-ray, Fourier-transform infrared, thermogravimetric analysis, and scanning electron microscopy. Additionally, the F-release kinetic profile was evaluated for 21 d in neutral and acid media with mathematical model analysis. Products with varying F-quantities were obtained, revealing specific release profiles. In general, there was a higher F-release in the acid medium, with emphasis on F-LDH-8. Fluoride-LDH and controlled fluoride delivery was successfully obtained, proving the potential of these nanomaterials as alternative anti-caries agents.