A facile methodology to modify polystyrene, to incorporate alkali soluble hydroxy groups, is reported. Polystyrene of well-defined number-average molecular weights in the range of 3000 to 50,000 were prepared by suspension polymerization at 80degreesC by varying the relative mole ratio of carbon tetrachloride, used as chain transfer agent. Polystyrenes were acetylated; the acetyl groups were converted to acetoxy groups, by Baeyer-Villiger oxidation, and hydrolyzed in a nonaqueous alkaline medium to generate hydroxy groups. The extents of modifications were monitored by infrared spectroscopy. The glass transition temperatures of poly(4-acetylstyrene-co-styrene), poly(4-acetylstyrene-co-4-acetoxystyrene-co-styrene), and poly(4-hydroxystyrene-co-4-acetylstyrene-co-styrene) were 107,134, and 142degreesC, respectively. The polymers were evaluated in photoresist formulations. (C) 2004 Wiley Periodicals, Inc.