A poly(vinyl alcohol)–cationic cellulose (PVA–CC) copolymer encapsulated SiO₂ stationary phase (PVA–CC–Sil) for hydrophilic interaction liquid chromatography (HILIC) is described. It is prepared simply by combining SiO₂ with a preformed PVA–CC solution, then filtering and curing thermally, finally generating a thin PVA–CC copolymer coating onto SiO₂. The preparation is easy to implement and no organic solvent is involved in. The phase shows obvious positive electrostatic character and typical HILIC character, exhibiting different selectivity relative to twelve commercial HILIC phases. Good running stability and a wide pH tolerance range (at least 10) are observed for PVA–CC–Sil. Excellent separation efficiency is obtained for model analytes (e.g. plate counts are ∼114 000 plates per m and ∼150 000 plates per m for ribose and 4-hydroxybenzoic acid, respectively). Good separation performance for saccharides of low or high degrees of polymerization by PVA–CC–Sil is also observed.