Molecular gel-forming glutamide lipid-grafted porous silica particles (Sil-SiDg) are designed and prepared as the stationary phase in high-performance liquid chromatography (HPLC) for molecular shape recognition. It was proven that the glutamide lipids formed a highly oriented structure on the silica surface and showed thermally reversible phase transition like self-assembled molecular gels even on the silica surface. Unprecedented excellent results were achieved in the separation of tocopherols (Vitamin E) using Sil-SiDg as the stationary phase in HPLC analysis.