The aim of this study was to regulate fluoride release from restorative resin containing NaF using N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (AMMS) and evaluate factors that regulate fluoride release from the resin. ESCA analysis, FT-IR measurements along with SEM observations demonstrated that a polysiloxane layer was formed on the surface of NaF treated with AMMS. Bis-GMA/TEGDMA resin containing NaF powder treated with AMMS released lower concentrations of fluoride for longer periods when compared with that containing untreated NaF. However, AMMS treatment of NaF was less effective for the regulation of fluoride released from the resin than γ-methacryloxypropyltrimethoxysilane (γ-MPTS) treatment, despite its higher hydrophobic polysiloxane layer formation. These findings may have been caused by the higher density of polysiloxane prepared with γ-MPTS than that prepared with AMMS. The present findings suggested, therefore, that alkoxysilane should be chosen based not only on hydrophobicity but also the density of polysiloxane to effectively regulate fluoride release from the restorative resin containing NaF.