Poly(acrylic acid) (PAA)/silica hybrids having imidazolium chloride [IL(Cl-)] moieties could be prepared by utilizing ionic interactions between anionic carboxylic acid groups of PAA and cationic imidazolium groups of silica phase. By removing PAA from the obtained hybrids, we could obtain hydrophilicity-controllable microporous hybrids by means of anion-exchange reaction of imidazolium moieties.