Drinking-water fluorosis is universal along coastal zones, and the seawater or brine water intrusion is occasionally supposed to enrich groundwater fluorine levels. However, there is no conclusive proof, and the laws and mechanisms remain ambiguous. Granite, the common fluorine-bearing rock, is selected and experimented upon to reveal the characteristics and laws of fluorine's leaching ability during the intrusion of seawater. The fluorine-leaching ability increases with the increasing ratios of seawater or brine water, the increasing levels of NaCl or NaHCO3, and the decreasing levels of CaCl2. Such results directly confirm that seawater or brine water intrusion, as well as the conditions of higher Na+, HCO3− and lower Ca2+, promotes fluorine-leaching ability from granite. The intensities of SiOSi, SiOFe, SiOAl bonds decrease but those of OH bonds increase with a higher ratio of seawater or brine water, the higher levels of NaCl or NaHCO3, and the lower levels of CaCl2. This indicates the more silicate dissolution and stronger OH-F exchange evoked by seawater or brine water intrusion are responsible for the higher fluorine-leaching from granite. Therefore, the process of seawater or brine water intrusion should be important for the groundwater enrichment dynamics along coastal zones.