A facile method to prepare a polar stationary phase for hydrophilic interaction chromatography (HILIC) was proposed by coating polyvinyl alcohol onto silica particles (PVA-Sil). A water or organic solvent-insoluble permanent PVA coating on the silica particle surface can be formed simply by dipping silica particles into a hot PVA solution and then settled from this solution, leaving a thin layer of PVA coating and frozen in a freezer. The PVA-Sil shields the silica core from solution erosion to some degree and the pH tolerance range was extended to 9.5 from 8.0 for bare silica. PVA-Sil demonstrated a good hydrophilic property for several kinds of polar compounds and ∼57000 m(-1) of plate count was achieved. This method can also be extended as a universal method to prepare various stationary phases with exchangeable functionalities by doping the desired ingredient in a PVA solution.