Layered magnesium–aluminum hydrotalcite (HT) were completely intercalated and stabilized with silicate anions. The silicate anion-stabilized HT retained the layered structure and possessed a high surface area of 530–540 m² g⁻¹ with needle-like particles 60 nm × 4 nm in dimension. The findings of FT-IR, powder XRD, TGA, DSC and ²⁹Si MAS-NMR revealed that silicate anions were intercalated and coated on the surface of layered HTs with the formation of a solid solution of magnesium silicate and HT. The resultant silicate-anion-intercalated materials are found to be promising catalysts for the synthesis of 1-phenoxy-2-propanol using phenol with propylene oxide.