Among several functional monomers, 10-methacryloxydecyl dihydrogen phosphate (10-MDP) bonded most effectively to hydroxyapatite (HAp). However, more hydrolysis-resistant functional monomers are needed to improve bond durability. Here, we investigated the adhesive potential of the novel fluoro-carbon functional monomer 6-methacryloxy-2,2,3,3,4,4,5,5-octafluorohexyl dihydrogen phosphate (MF8P; Kuraray Noritake Dental Inc., Tokyo, Japan) by studying its molecular interaction with powder HAp using solid-state nuclear magnetic resonance (H-1 MAS NMR) and with dentin using x-ray diffraction (XRD) and by characterizing its interface ultrastructure at dentin using transmission electron microscopy (TEM). We further determined the dissolution rate of the MF8P_Ca salt, the hydrophobicity of MF8P, and the bond strength of an experimental MF8P-based adhesive to dentin. NMR confirmed chemical adsorption of MF8P onto HAp. XRD and TEM revealed MF8P_Ca salt formation and nano-layering at dentin. The MF8P_Ca salt was as stable as that of 10-MDP; MF8P was as hydrophobic as 10-MDP; a significantly higher bond strength was recorded for MF8P than for 10-MDP. In conclusion, MF8P chemically bonded to HAp. Despite its shorter size, MF8P possesses characteristics similar to those of 10-MDP, most likely to be associated with the strong chemical bond between fluorine and carbon. Since favorable bond strength to dentin was recorded, MF8P can be considered a good candidate functional monomer for bonding.