Hainan, a well-known center of tropical agricultural production in south China, has received little attention regarding groundwater fluoride contamination. This study investigates the occurrence of fluoride in the western coastal area of Hainan Island and discusses factors affecting groundwater fluoride contamination in various aquifers and areas with different land-use types using hydrochemistry and multivariate statistical analysis. A total of 100 groundwater samples were collected from the western coastal area of Hainan Island. The results show that the groundwater fluoride concentration is as high as 4.18 mg/L and that F⁻-high (>1 mg/L) groundwater accounts for 9% of total groundwater. The proportion of F⁻-high fissure water is about two times that of F⁻-high pore water. Among the different land-use types, the proportion of F⁻-high groundwater from highest to lowest is as follows: bare land > cultivated land > woodland > construction land > grassland. The main factor affecting fluoride in pore water is the leaching of fluorine/aluminum-containing minerals such as phlogopite and calcite in the vadose zone, which is characterized by the co-enrichment of fluoride and aluminum in pore water. The leading cause of fluoride in fissure water is the leaching of fluorine-containing fertilizers, and continuous irrigation promotes the cation exchange of sodium, strontium, and calcium, which is characterized by the co-enrichment of fluoride with sodium and strontium in fissure water. Consequently, it is advised to minimize the excessive use of fluoride fertilizers and increase groundwater quality monitoring in order to decrease the emergence of F⁻-high groundwater in the western coastal area of Hainan Island.