The synthesis and characterization of poly(4-hydroxystyrene) (PHS) and poly(4-vinylphenol) (PVPh) by the polymer modification route are reported. Polystyrene prepared by free-radical and anionic polymerization was acetylated quantitatively to poly(4-acetylstyrene) (ACPS) with acetyl chloride and anhydrous aluminum trichloride in carbon disulfide. The acetylation worked equally well in a mixture of 1,2-dichloroethane (DCE) and nitrobenzene containing largely DCE. The extent of the acetylation was estimated by H-1 NMR. The oxidation of ACPS was carried out with various oxidizing agents and reaction conditions. The peracetic acid oxidation in chloroform resulted in quantitative oxidation to poly(4-acetoxystyrene) (APS) as estimated by H-1 NMR spectroscopy. The treatment of APS with hydrazine hydrate in dioxane resulted in the formation of PVPh. Deacetylation occurred with equal versatility in a mixture of aqueous sodium hydroxide and tetrahydrofuran. All the polymers were characterized via gel permeation chromatography, IR, UV,H-1 NMR, and C-13 NMR spectroscopic techniques. This is the first report on the synthesis of ACPS, APS, and PHS of reasonably narrow molecular weight distributions or otherwise by the polymer modification route.