A facile synthesis of linear monodisperse hydroxyl-containing polystyrene, poly{styrene-co-[p-(1-hydroxyethyl)styrene]} acid poly{styrene-co-[p-(2-hydroxypropan-2-yl)styrene]}, was carried out via chemical modification of polystyrene by a two-step procedure, i.e. monodisperse polystyrene was acetylated under mild conditions, followed by processes of reduction with LiAlH4 and addition with CH3MgBr, respectively. H-1 NMR and FTIR spectra showed that in both cases, the reaction of acetyl to hydroxyl is complete. Size exclusion chromatography demonstrated that both molecular weight and monodispersity of the final products were basically unchanged.